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WILDER D. BANCROFT AND NELSON F. MURPHY Department of Chemistrg, Cornell University, Ithaca, New YorL

Received August SO, 19Sq

In suitably acid solutions and with suitable concentrations hydrogen peroxide reduces the following: cobaltic sulfate to cobaltous sulfate; lead peroxide to lead sulfate; permanganic acid, manganese dioxide, and man- ganic sulfate to manganous sulfate; chlorine and hypochlorous acid to hydrochloric acid; bromic acid to hydrobromic acid and bromine; chromic acid to chromic sulfate; chloric acid at 80°C. to hydrochloric acid and chlorine; hypobromous acid to hydrobromic acid; thallic sulfate to thallous sulfate; bromine to hydrobromic acid; periodic acid to iodic acid; iodic acid to iodine; 95 per cent nitric acid to oxides of nitrogen; bismuth pent- oxide to bismuth trioxide; pentavalent vanadium to tetravalent vanadium. In suitably acid solutions and with suitable concentrations hydrogen peroxide oxidizes the following: hydrochloric acid to chlorine; hydrobromic acid to bromic acid; hydriodic acid to iodine and to iodic acid; ferrous chloride to ferric chloride; nitrous acid to nitric acid; mercurous nitrate to mercuric nitrate; silver to silver sulfate; tetravalent vanadium to Pentavalent vanadium; cuprous chloride to cupric chloride; ferrocyanic acid to ferricyanic acid; stannous chloride to stannic chloride; hydroxyl- amine and nitrous acid to nitric acid; nickel and lead to the corresponding sulfates. In suitably alkaline solutions and with suitable concentrations hydrogen peroxide reduces the following: potassium permanganate and manganate to manganese dioxide; potassium ferrate to ferric oxide; silver peroxide and silver oxide to silver; potassium hypobromite to bromide ; potassium ferricyanide to ferrocyanide; nickelic oxide to nickelous oxide; bismuth pentoxide to bismuth tetroxide (or Bi40,) ; potassium periodate to iodate; and potassium hypoiodite to iodide. It is said, though wrongly, to re- duce mercuric oxide to mercurous oxide. In suitably alkaline solutions and with suitable concentrations hydrogen peroxide oxidizes the following: potassium cyanide to cyanate; sodium sulfite to sulfate; lead and lead monoxide to lend peroxide; bismuth tri- oxide to bismuth tetroxide (or Bi407); cobaltous oxide to cobaltic oxide or peroxide; manganous and manganic oxides to manganese peroxide ; vanadium tetroxide to vanadium pentoxide; chromic oxide to potassium








chromate; thallous oxide to thallic oxide; nitric oxide and potassium nitrite to potassium nitrate; cuprous oxide to cupric oxide; hydroxylamine to nitrogen; ferrous and stannous oxides to ferric and stannic oxides, respec- tively; zinc to sodium zincate. It is not claimed that this is a complete list of the oxidations and reduc- tions with hydrogen peroxide, but these instances will suffice to show the

apparent complexity of the problem. So far as the theoretical side of the subject is concerned, the literature is in a state of chaos because the “mis- leading experiment” has tripped up everyone. The problem has not been and cannot be solved by a phenomenological study alone. The Baconian method is not adapted to this sort of work. Fredenhagen (11) and Bornemann (4) both accept Haber’s view of two potentials for hydrogen peroxide in acid solution, a reducing potential at about Et, = +0.8 volt and an oxidizing potential at about Eh = +1.4 volts. Bornemann says that “a substance with a potential in a dilute acid solution smaller than Eh = $0.8 volt, such as hydriodic acid with about E,, = 0.5 volt, can only be oxidized by molar hydrogen peroxide. If the potential of the reacting substance is higher than Eh = +1.4 volts, such as Eh = +1.5 volts for potassium permanganate, there can only be reduction by hydrogen peroxide. Substances with potentials between Eh = +0.8 volt and Eh = +1.4 volts may be either reduced or oxidized by hydrogen peroxide. When the nature of the substance permits of either reduction or oxidation, which will happen or whether both will happen simultaneously to an appreciable extent depends only on relative reaction velocities; catalytic agents play an important part within this range.” Our experiments show that there are no true electromotive forces for dilute hydrogen peroxide in acid solution at about EJ,= $0.8 volt and about Eh = +1.4 volts, and that there is no range within which it is a question of reaction velocity whether reduction or oxidation occurs. There is also no true electromotive force for hydrogen peroxide at about Eh = +1.66 volts as postulated later by Haber (16). In the same way the normal electrode potential Eh = +I .8 volts, as given by Kremann and Muller (18) for the alleged reaction H202+2H = 2H20, is entirely mythi-


Bray (5) gives Eh = +1.78 volts.

If the true electromotive force, re-

ferred to the normal hydrogen electrode, for any oxidizing or reducing agent in any solution is larger than the true electromotive force of hy- drogen peroxide in the same solution, that substance will be reduced by hydrogen peroxide. If the true electromotive force, referred to the normal

hydrogen electrode, of any oxidizing or reducing agent in any solution is smaller than the true electromotive force of hydrogen peroxide in the same solution, that substance will be oxidized by hydrogen peroxide. As will

The real relation is quite simple.







be shown later, the reason why this relation has not been clear from the beginning is that people talked about measured electromotive forces and not about true electromotive forces. In tables 1 and 2 are given data for some of the oxidizing and reducing agents which are on record as reacting with hydrogen peroxide. The figures under E,(Murphy) were obtained at Cornell and are measurements made against the normal calomel electrode. Platinum wires were used and were heated electrically (34) to bring them approximately to equilib-

rium. The plus sign denotes that the calomel electrode is anode. The E, data have been converted into Eh values by adding 0.300 volt, with no other correction for liquid-junction potentials except for the reversible reaction between iodic acid and iodine, where the measurements were made against hydrogen in molar sulfuric acid. The E, data are not neces- sarily right, but they are comparable. The Eh data, not based on our E, measurements, are taken from the literature and are not comparable among themselves or with the Cornell data. So far as can be judged, they are right relatively to hydrogen peroxide; but no guarantee can be given that they are right absolutely or right relatively to each other.

They will

To many people this will seem a deplorable state of affairs.

feel that we should have corrected all these data and that we should have given our data at least to millivolts and probably to tenths of millivolts.

T. W. Richards once said that to measure a thing ten times as accurately meant one hundred times the work. There is a great deal of time wasted

on unnecessary accuracy in measurements. If we wish to know whether hydrogen peroxide will oxidize ferrous chloride at all, we must determine the electromotive force of a practically pure ferrous chloride solution. If we wish to know whether hydrogen peroxide will oxidize ferrous chloride completely, we must determine the electromotive force of a practically pure ferric chloride solution. The spread in this case is more than 0.2 volt, so an accuracy of millivolts means nothing. The corresponding spread for tetravalent to pentavalent vanadium is apparently nearly half

a volt. From the admittedly inaccurate data in table 1 we shall see that

the best measurements of the electromotive force for appreciable con- centrations of hydrogen peroxide in acid solution may be roughly 0.3- 0.4 volt too low. There will undoubtedly come a time when it will be desirable to measure these electromotive forces to millivolts or less. For the moment the im- portant thing is the determination of general relations. That has been overlooked entirely in the forty years of exact measurements and elaborate thermodynamics. It is usually stated that it is a waste of time to measure t'he electromotive forces of practically pure ferrous sulfate and ferric sul- fate, because the electromotive force measurement means nothing unless we define the concentrations of the reaction products. This may be true







theoretically; but we deny it very often when we do a potentiometric

analysis. It would be a distinct help if people made and tabulated the electromotive forces which are involved in potentiometric analyses, in- stead of ignoring them or treating them as belonging in an entirely inde- pendent chapter.

clear from table 1 that, in approximately molar solutions of

hydrochloric or sulfuric acid, all oxidizing and reducing agents having an

electromotive force for the reaction and concentrations in question larger than about Eh = +1.16f0.3 volts are reduced by hydrogen peroxide. All having an Efi value smaller than about 1.16f0.03 volt are oxidized


It .is quite

Behavior of hydrogen peroxide in acid solutions

E, (Murphy) data are mostly in M HC1 or M HzS04.

Parentheses denote that the

enclosed constituent is present in relatively small amounts













$1 .79








+1.54 fl.237
















+1.34 tl.058




Ferrocyanic acid-+ferri-

Br2+ (HBr)



cyanic acid












* One-way reactions; not strictly reversible. t Measured directly and not calculated.



+O ,850


+O .790






+O .37



+O. 49

+o .19







by hydrogen peroxide. This does not mean that hydrogen peroxide will oxidize ferric chloride higher because the reaction measured is Fe''*Fe"'. If we should or could measure the reaction Fe'I1$FeVr that electromotive force would be found to be larger than Eh = f1.16 volts. The data in table 1 show that the true electromotive force of hydrogen peroxide in a solution approximately molar with respect to hydrogen ion is about Eh = S1.16k0.3 volts, and that there is no intermediate range within which relative reaction velocities determine whether oxidation or reduction will occur. The directly measured value of about Eh = +0.8 volt and the deduced value of Eh = +1.66 volts go by the board. It is quite clear from table 2 that, in approximately molar solutions of






potassium hydroxide, all oxidizing and reducing agents having an electro- motive force for the reaction and concentrations in question larger than about Eh = +0.30=t0.03 volt are reduced by hydrogen peroxide. All having an electromotive force smaller than about Eh = +0.30f0.03 volt are oxidized by hydrogen peroxide, with the exception of potassium iodide to potassium iodate, which will be discussed later. When an oxidation or reduction can only go one way under the conditions of the experiment, the predictions apply only to the reaction measured. We can obtain approxi-

TABLE 2 Behavior of hgdrogen peroxide iii alkaline solutions E, (Murphy) data are mostly in M KOH



ipproxi- E, nate EA (Murphy)






mate El
















,73 +O







+O .41











+O ,294











+O. 279





.51 +O



+o. 11




+o. 10



.51 +O.



+O .08





+0.34 +O ,038
















* One-way reactions; not strictly reversible.

mate values for the oxidation of sulfurous acid to sulfuric acid and for the oxidation of alkaline sodium sulfite to alkaline sodium sulfate, but the reverse reaction does noktake place at all in alkaline solutions; in acid solutions it takes place only at very high concentrations of sulfuric acid. The data in table 2 show that the true electromotive force for hydrogen peroxide in a solution approximately molar with respect to hydroxyl ion is about Eh = +0.3f0.03 volt, and that there is no intermediate range within which relative reaction velocities determine whether oxidation or reduction will occur. This compares with an apparent value as measured directly and not corrected for diffusion potentials of about Eh = +0.04 volt. It must be remembered that the value of Eh = f0.3f0.03 volt con-








tains the acid-alkali liquid-potential difference, which is not present in the value of Eh = +l,l6=t0.03 volts. Consequently these two values cannot be compared directly. There is independent evidence for Eh = +1.16 volts being somewhere near the true electromotive force for hydrogen peroxide in approximately molar hydrochloric acid or sulfuric acid. No one has ever obtained the theoretical value of 1.23 volts for the oxyhydrogen gas cell, but values up to 1.15 volts have been measured by independent observers, Over fifty years ago Traube (48)showed that hydrogen peroxide is formed when oxygen is reduced at the cathode. Both G. N. Lewis (21) and Haber (15) drew the natural conclusion that the primary reaction in the oxyhydrogen gas cell is the formation of hydrogen peroxide. This view has not yet been accepted (14), but it is unquestionably right (47). Richarz and Lonnes (35) obtained an 88 per cent current efficiency for hydrogen peroxide exclusive of what had been lost by catalytic decomposition, Quite recently Fisher and Kronig (7) have obtained a 93.5 per cent current efficiency under favorable conditions. It seems to be practically certain that 100 per cent current efficiency would be obtained if catalytic decom- position could be avoided. Another argument in favor of this is that the decomposition-voltage curve for sodium peroxide between platinum electrodes is of the same type as that for copper sulfate between copper electrodes, an approximately straight line starting from the origin. This means that the reactions at the two electrodes are the same in fact but opposite in sign. Consequently the value of Eh = +1.16+0.03 volts must be very close to the true value for the reaction H2+Oz = HYOz in a suitably acid solu- tion. It would be more difficult to prove that E* = +0.30f0.02 volt is approximately the true value for alkaline solutions because of the higher rate of catalytic decomposition of hydrogen peroxide in alkaline solutions. This is not necessary, however, because the close agreement between the chemical and electrical results in acid solution establishes the validity of the chemical method. Fredenhagen (12) objected to Haber's calling hydrogen peroxide a reducing agent, because Fredenhagen found that hydrogen peroxide oxi- dizes ferrous chloride completely, even though the measured electromotive

force of a hydrogen peroxide electrode relative to the ferro-ferric electrode is the same as that of an acidified solution containing about 10 per cent

molar ferrous chloride and 90 per cent molar ferric chloride.

two mistakes here. The true electromotive force of a hydrogen peroxide electrode is larger than that of a ferric chloride solution, and consequently hydrogen peroxide should oxidize ferrous chloride completely. Also, if

Fredenhagen had made up a cell PtllO per cent H2Oz in N/10 HCllN FeC13 in NjlO HClIPt, he would have observed a reduction of ferric chloride in the cell, as we did.

There are






Ferrous salts combine with a,d-dipyridyl (19) to give complexes in which the concentration of ferrous ions is apparently vanishingly small. This makes the ferric salt a stronger oxidizing agent; consequently it is not surprising that hydrogen peroxide reduces ferric salts quantitatively in presence of a,a'-dipyridyl. As we had none of this substance, we could not make any electromotive force measurements, but they would un- doubtedly have fallen in line. It has long been known that hydrogen peroxide in alkaline solutions reduces potassium ferricyanide to potassium ferrocyanide. All who have measured the electromotive force of this re- action have found it come out as it should relatively to our value for hy- drogen peroxide. Since the formation of hydrogen peroxide is the primary reaction in the oxyhydrogen gas cell, it must take 2 faradays to form one gram-molecular weight of hydrogen peroxide. Consequently the oxygen anion concerned must be Oi, corresponding to the mercurous cation Hgi. This is in accord with the experiments of Tanatar (46),who determined the volumes of oxygen set free at the anode from certain hydrogen peroxide solutions and those set free in a sulfuric acid coulometer. The conditions could be so adjusted that two volumes of oxygen were set free from hydrogen per- oxide as against one volume of oxygen from the coulometer. This was after correcting for oxygen set free in consequence of catalytic deconiposi- tion. In an alkaline barium peroxide solution the anion must be bivalent diatomic oxygen. If we have a case of reversible oxidation and reduction, such as Fee+ Fe"', the extreme values for a practically pure ferrous salt solution and for a practically pure ferric salt solution will be either on the same side of the true hydrogen peroxide potential for that solution or on opposite sides. If both are on the same side, the reaction will run to an end. Hydrogen peroxide oxidizes ferrous salts completely to ferric salts either in acid or in alkaline solutions. Permanganate is reduced completely both in acid and in alkaline solutions. Lead peroxide is reduced completely to lead sulfate in acid solutions, and lead monoxide is oxidized completely to lead dioxide or sodium plumbate in alkaline solutions. Hydriodic acid is oxidized completely to iodine in acid solutions. If the two extreme values lie on opposite sides of the true electromotive force for hydrogen peroxide in that soluti'on, a state of equilibrium occurs. Liquid bromine with a low concentration of hydrobromic acid gives a value of Eh = +I .26 volts and is reduced by hydrogen peroxide. Bromine with a high concentration of hydrobromic acid gives a value of Eh = +1.09 volts, and the hydrobromic acid is oxidized by hydrogen peroxide. The zero point at which traces of hydrogen peroxide are in equilibrium with liquid bromine and hydrobromic acid is at about Eh = f1.16 volts, apparently between +1.17 and +1.15. The conversion of iodine into iodic acid and back is a very good illustra-








tion of this. As the literature at present is in a hopelessly confused state, this case brings out the advantage of our viewpoint. Iodine dissolved in M sulfuric acid is converted nearly completely into iodic acid. The reverse reaction does not take place to an extent which can be detected by the casual observer. If one adds a little carbon tetrachloride to a solution of iodic acid in 2 normal sulfuric acid before adding the hydrogen peroxide, the existence of an equilibrium will be shown by the development of a pink color in the carbon tetrachloride. Using dilute hydrogen perox- ide a pink color develops with M/2 and M/50 iodic acid but not with M/200 iodic acid. When 30 per cent hydrogen peroxide is added, a pink color is obtained even with M/2000 iodic acid. This shows again that hydrogen peroxide is a stronger reducing agent in more concentrated solu- tion. If the carbon tetrachloride is added after the hydrogen peroxide has decomposed completely, no pink color is obtained even with M/2 iodic acid. If one adds iodine crystals to a solution of hydrogen peroxide in 2 normal sulfuric acid, the solution does not become colored by the iodine and the oxidation to iodic acid takes place very slowly. This apparent paradox is due to the catalytic decomposition of the hydrogen peroxide at the sur- face of the iodine crystals. These crystals become coated with a film of ogygen, which protects them pretty well from the solvent action of the solution. The rate of oxidation can be accelerated by stirring the solution vigorously, or by starting with a saturated solution of iodine in carbon tetrachloride and adding excess iodine. The zero point is about Eh = ql.16 volts, apparently between $1.17 and $1.15. Auger (1) obtained visible amounts of iodine by starting with a dilute iodic acid solution, We have improved on that technique by starting with a concentrated potassium iodate solution, adding a few drops of hydrochloric acid or sulfuric acid, and then adding 30 per cent hydrogen peroxide. A heavy precipitation of iodine occurs, which stops when the solution becomes neutralized. Further addition of hydrochloric acid causes additional precipitation of iodine. If concentrated hydrochloric

acid is added, the iodine is oxidized to iodic acid by the hydrogen peroxide. If caustic potash is then added, iodine will come down again on addition of hydrogen peroxide, provided the solution has not become too dilute. This makes a very striking lecture experiment. In our experiments the change from reduction to oxidation occurs at about pH = 1.2 to 1.4, apparently regardless of whether one uses hydro- chloric acid or sulfuric acid. If one adds the acid in several portions, each one after the preceding portion has been neutralized, one can get a

good deal of reduction.

the pH drops below 1.2 and there is practically no reduction. Since the

change occurs at approximately the same pH both with hydrochloric acid

If the same amount of acid is added all at once,






and with sulfuric acid, the intermediate formation of iodine monochloride

or trichloride cannot be of vital importance as Auger assumed it to be. The electromotive force measurements on periodic acid and potassium periodate confirm the chemical findings by Tanatar (45) that hydrogen peroxide reduces periodic acid and sodium periodate to iodic acid and sodium iodate, respectively. With potassium iodide and potassium iodate

we ran into a serious difficulty which we had not foreseen, although per-


mean that sodium peroxide oxidizes alkaline potassium iodide to potassium

iodate. In spite of all our efforts to the contrary, we were forced to con- firm the results of our predecessors that sodium peroxide produces prsc- tically no potassium iodide from potassium iodate.

One can

obtain an electromotive force measurement for sodium sulfite as a reduc- ing agent and one can oxidize sodium sulfite to sodium sulfate; but one cannot reduce sodium sulfate to sodium sulfite. In the presence there- fore of a suitable reducing agent, both sodium sulfite and sodium sulfate would be practically stable. The conversion of sodium iodide to sodium iodate is not quite a parallel case to that of sodium sulfate to sodium sulfite, because a sufficiently strong oxidizing agent, such as ozone, will oxidize alkaline sodium iodide to sodium iodate (20) and even to sodium periodate

(36). We have found that alkaline permanganate is bleached by alkaline sodium iodide. The difficulty with the hydrogen peroxide is that potas- sium hypoiodite is the first stage in the oxidation of iodide, and that hy- drogen peroxide reduces hypoiodite. To oxidize alkaline potassium iodide to iodate, one must use an oxidizing agent, such as ozone or alkaline per- manganate, with a higher oxidizing potential than alkaline potassium hypoiodite. On the reduction side there is no difficulty. Either an alkaline hydrazine or hydroxylamine solution will reduce alkaline potas- sium iodate to iodide. The reason that hydrogen peroxide can oxidize

hydriodic acid to iodic acid is that the first stage is the oxidation to iodine.

A strong enough oxidizing agent should oxidize alkaline sodium chloride

to sodium hypochlorite and sodium chlorate. Alkaline permanganate

will not do it, and we have not tried ozone.

We can now consider the problem of where the oxygen gas comes from when hydrogen peroxide reacts with lead peroxide in sulfuric acid solution. This is simpler than the case of permanganate, and just as typical. There are many differences in detail, but, speaking broadly, there are two schools of thought. One school-led originally by Schonbein, Brodie, and Berthelot-believes that half the oxygen gas comes from the lead peroxide and half from the hydrogen peraxide. The other school-led originally by Weltzien, Traube, and Baeyer-believes that all the oxygen gas comes from the hydrogen peroxide and none of it from the lead peroxide.

haps we should have.

The electromotive force of Et, =


A way out of this impossible situation was found at last.

Fluorine will do it.







Most textbooks adopt the first view-that of Schonbein, Brodie and Berthelot-for no apparent reason. Roscoe and Schorlemmer (38) say:

“The oxides of metals such as gold, silver, and platinum immediately cause decomposition of hydrogen dioxide into water and oxygen even in dilute aqueous solutions, and the oxides themselves are simultaneously reduced to the metallic state, the reduction with silver oxide being repre- sented by the equation:

Ag2O + H2Oz = 2Ag + H2O + 02

“We have here the remarkable phenomenon of a powerful oxidizing agent exerting a reducing action on metallic oxides with formation of the metal. The explanation of this fact is, however, not far to seek. The above-named metals only combine somewhat feebly with oxygen, and their oxides decompose easily into the elements. When they are brought into contact with hydrogen dioxide, which contains one atom of oxygen but feebly united, mutual reduction takes place, the one atom of oxygen in the dioxide combining with one atom of oxygen in the metallic oxide to form a molecule of free oxygen.” If we ear-mark the oxygen which is to go off as gas by italicizing it, we can make clear the difference between the two points of view. Ac- cording to Roscoe and Schorlemmer one should write the equation:

Ag20+ H20.0 = 2Hg + HzO + 02 (alkaline)


PbO.0 + H20.0 = PbO + H20+ 02 (acid)

According to the other view, which we endorse, one should write:

Ag2O + HzOz = 2Ag + H20 + O2 (alkaline)


PbO2 + H202 = PbO + HzO + O2 (acid)

The oxidation-not be written :

HzO2 + 020 = HzO + 202

We will now give the reasons (39) for adopting the view put forward by Weltzien, Traube, and Baeyer. Hydrogen peroxide may be considered as dissociating reversibly to a very slight extent into monatomic, electri- cally neutral hydrogen and activated diatomic oxygen: H202e 2H + 0.0. Reductions are effected by the monatomic hydrogen and oxidations by the


hydrogen peroxide

by ozone should








activated diatomic oxygen, which differs from molecular oxygen by only having one bond between the oxygens. It is an unsaturated oxygen molecule.

HzS04 1 H2SO4, PbOz I Pb, the current

will flow from left to right through the cell, lead peroxide will be reduced to lead sulfate at the cathode, and two oxygens will be evolved at the platinum anode for one gram-molecular weight of lead peroxide reduced. The anode reaction is precisely similar to the one studied quantitatively by Tanatar. In this case there can be no question but that the two oxy- gens come from the hydrogen peroxide and neither one from the lead peroxide. Similar cells can be set up in all cases in which the error in the potential measured at the platinum electrode, due to the difference between the apparent and true electromotive force of hydrogen peroxide or of the reacting substance, is not sufficiently large to obscure things. VE'ith platinum in acidified hydrogen peroxide against platinum in acidi- fied permanganate,,manganese dioxide, or chromic acid, the peroxide elec- trode is the anode, as it should be. With platinum in alkaline hydrogen peroxide against platinum in alkaline permanganate, the hydrogen peroxide electrode is the anode, as it should be. With platinum in alkaline manganous hydroxide against platinum in alkaline hydrogen peroxide, the hydrogen peroxide electrode is the cathode. Theoretically it should be the cathode, when platinum in alkaline lead monoxide is the other electrode; but actually that is not the case. Appar- ently the reason why this experiment is unsuccessful with normal alkali is that hydrogen peroxide is catalyzed so rapidly by platinum in such a solution that it is impossible to build up the proper potential at the elec- trode. Once the cause of the trouble was recognized, it was easy to get around the difficulty. Alkaline hydrogen peroxide oxidizes manganous hydroxide to manganese dioxide and is therefore a stronger oxidizing agent than alkaline manganese dioxide. A cell was accordingly made up Pt I PbO, N KOH I N KOH, MnOz [ Pt. The manganese dioxide elec- trode is the cathode; consequently the stronger oxidizing agent, hydrogen dioxide, would also be at the cathode if the catalytic decomposition were eliminated. A similar arrangement made it possible to show that alka- line chromic oxide and alkaline cobaltous oxide are really anodic to hydro- gen peroxide of the same general alkalinity. In every case the current in an electrolytic cell containing hydrogen peroxide flows in the direction predicted by the chemical reaction, or can be made to do so by eliminating the unessential disturbing factors. It is not safe to say that the type of reaction as postulated by Schonbein and Brodie cannot be arranged as an electrolytic cell, but no one has yet done it and it is not clear what would be anode and what cathode. It has also never been explained why hydrogen peroxide and lead peroxide or manga-


If we arrange a cell, Pt IHzOz in







nese dioxide should be compatible in alkaline solution and incompatible in acid solution. In the reaction between barium peroxide and iodine, BaOz + IZ= Bar2 + 02, all the oxygen must come from the peroxide. We may therefore consider the question of the source of the oxygen gas

as settled in the way it should have been settled a long time ago-in favor of the view advanced by Weltzien, Traube, and Baeyer. As late as 1858 Schonbein (40)explained the reaction HzOz+ Clz = 2HC1 + OZon the basis that chlorine was murium peroxide and not an element. An additional argument is to be found in the experiments of Fowler and Grant (10) on the effect of heating lead peroxide with potassium chlorate. From Schonbein’s point of view the result should have been evolution of oxygen with the formation of lead monoxide and potassium chloride, both substances losing oxygen. Actually there was a nearly quantitative oxidation of potassium chlorate to potassium perchlorate. When dry sodium peroxide is ground with iodine and heated suitably, there is formation of sodium periodate (17). Raikow (33) takes the ground that a substance cannot have the same formula as a reducing agent and as an oxidizing agent. He therefore con- siders that the reducing agent is HO-OH and that the oxidizing agent is

We have postulated the

reversible dissociation H202e 2H + 0-0. When hydrogen peroxide acts as a reducing agent, we have 2H reacting with the substance to be reduced and the 0-0 going off as molecular oxygen. When hydrogen peroxide acts as an oxidizing agent, the activated oxygen reacts both with the substance to be oxidized and with the monatomic hydrogen. For

lead oxide in alkaline solution we have, for instance:

H2=0 : :O=.

This seems quite unnecessary.

2H + 0-0

+ PbO = H2O + PbO2

For hydriodic acid in acid solution we have as the first stages:

2H + 0-0

+ HI = HzO + HI0

Starting with this point of view one cannot admit that the catalytic decomposition of hydrogen peroxide can be represented by the equation HzOz-+ HzO + 0. It must be that one molecule of hydrogen peroxide reduces a second one in exactly the same manner that one molecule of

The equation

hydrogen peroxide reduces one molecule of lead peroxide. would be written:

HzOz + HzOz = 2Hz0 + Oz

After this conclusion had been reached independently, it was a great pleasure to find that Wieland (51) had said the same thing more than a dozen years ago. He considers that the first stage in the catalytic decom-







position is the dehydrogenation of one molecule, the hydrogen from which reacts very rapidly with a second molecule. Wieland writes the equations :

HO*OH+ 0:O + 2H

HOmOH + 2H -+


The only difference between Wieland’s point of view and ours is that we postulate a reversible dissociation and consequently the formation of 0-0 with subsequent formation of molecular oxygen, 0: 0. If hydrogen peroxide decomposed, as is usually assumed, according to the equation Hz02---f H20 + 0, it would necessarily be one of the most powerful oxidizing agents, because it would be setting free nascent oxygen which is, next to fluorine, the most powerful oxidizing agent that we have at ordinary temperatures. As a matter of fact this work was started with the idea that one could do chemical.electrolyses with hydrogen peroxide nearly as well as with fluorine. That view was given up when it was found experimentally that hydrogen peroxide is a rather weak oxidizing agent, This is quite reasonable now that we see that what is first evolved is 0.0 and not 0. While molecular oxygen is not as effective an oxidizing agent as hydrogen peroxide, because of its inertness, molecular oxygen in contact with platinum is a stronger Oxidizing agent than hydro- gen peroxide, though not so convenient a one. If one writes hydrogen peroxide with the unsymmetrical formula, one gets into difficulty because the dissociation HzO:0 2H + 0:0 gives molecular oxygen. The catalytic decomposition by platinum may be written :

H,Oz + Pt = Pt(2H) + 02 H202 + Pt(2H) = Pt + 2H20

The measured reaction is therefore monomolecular. For this particular case we have practically eliminated the distinction between contact cataly-


sis and reaction catalysis made by Bray (5) and Livingston (22).

do not agree with the conclusions drawn by Bray and Livingston in regard to catalysis in homogeneous solutions, though their premises are


They have shown “that in acid solution hydrogen peroxide oxi-

dizes bromide to bromine, and reduces bromine to bromide, and that these two reactions can take place independently in the same solution, When the rates of these two compensating reactions are equal, the net

This consti-

result is the catalytic decomposition of hydrogen peroxide.

tutes a ‘steady state,’ in which the concentrations of bromine, bromide,

and acid remain constant in a single experiment.” Bray postulates two electromotive forces for molal hydrogen peroxide in molal acid, a reducing one of E* = +0.56 volt and an oxidizing one of Eh = +1.78 volts. He considers that an oxidation-reduction catalysis of







hydrogen peroxide occurs when the electromotive forces of the oxidation-

reduction couple lie between these two limiting values. In the first place, the steady state is not really one, because the concentrations vary with

the concentration of hydrogen peroxide.

until all the hydrogen peroxide is used up, the final electromotive force involved is ours of E,, = +1.16 volts and not the hypothetical ones given by Bray. What Bray should have said is that one gets an oxidation-reduction catalysis of hydrogen peroxide when one electromotive force lies above Eh = +1.16 volts and the other below it. Bray came to grief with the ferric salt oatalysis of hydrogen peroxide, because there is no evidence of any reduction of ferric ion to ferrous ion by hydrogen peroxide. Bray mentions the possibility of oxidation to ferrate, but does not dwell on it. We explain the catalysis by the temporary formation of the instable ferric acid. When neutral hydrogen peroxide is added to neutral ferric chloride solution, a dark red color is formed temporarily, which is undoubtedly due to a higher valence of iron.

If the catalysis is to continue

This is confirmed by the work of Bohnson (3) and Robertson (37), who photographed the absorption spectra of solutions of ferric chloride alone, barium ferrate dissolved in acetic acid, potassium ferrate, and mixtures of hydrogen peroxide and ferric chloride. There is a striking similarity be- tween the bands for the two ferrates and those for the reaction mixture. On the other hand, a solution of ferric chloride shows no such character- istic bands in the yellow and green, and is totally opaque to the violet. When hydrogen peroxide is added to the ferric chloride, transmission of violet lines takes place and absorption bands appear in the yellow and green. One of the very interesting things about hydrogen peroxide is the alleged presence of perchromic acid in the blue solution obtained temporarily by adding hydrogen peroxide to a suitably acidified chromic acid solution.

It is a regular experiment in all introductory courses in chemistry.


the name “perchromic acid” implies, most people consider that chromium has been oxidized to a higher valence than it has in chromic acid. Friend

(13) writes the formulas for the perchromic acids as

giving chromium a valence of seven. As a matter of fact, the evidence against the existence of a higher oxide

Chromic acid does not

of chromium in perchromic acid is conclusive.






bleach acidified permanganate and is therefore not oxidized by it, although acidified permanganate is a stronger oxidizing agent than chromic acid. The blue compound does bleach acidified permanganate even after the free hydrogen peroxide has been removed.

Platinum causes

the blue color to fade more rapidly than it would otherwise, but takes quite a while. In spite of this we have been unable to produce the blue oxide by electrolysis with a platinum anode. The only agents which will give rise to the blue color are hydrogen peroxide and compounds which set free hydrogen peroxide, such as ozomolybdic acid, pervanadic acid, pertitanic acid, pertantalic acid, perzirconic acid, peruranic acid, per- tungstic acid, perboric acid (8), copper peroxide, mercury peroxide, etc. These are substances whose scientific names do not describe the products. These experiments were done before we had read the paper by Moissan (28), but our line of reasoning is identical with his. Consequently the blue compound is not a higher oxide of chromium, any more than barium peroxide involves a higher valence of barium. The blue compound is either an addition product or a metathetical product of chromic acid and hydrogen peroxide. It cannot possibly be chromium with a valence of seven, as many people assume. Addition of hydrogen peroxide to a chromic acid electrode does not raise the potential even when a blue color is formed temporarily. Spitalsky (44) found that in 3 normal sulfuric acid hydrogen peroxide reduces chromic acid practically instantaneously to chromic sulfate. Traube (49) showed that persulfuric acid dissolved in 70 per cent sulfuric

acid causes chromic acid to go to chromic sulfate because a sulfuric acid of this concentration converts persulfuric acid rapidly into hydrogen peroxide. With persulfuric acid dissolved in a 40 per cent sulfuric acid no appreciable reduction occurs. This means that persulfuric acid does not oxidize chromic acid to any of the so-called perchromic acids.

Lead peroxide does not give rise to the blue color.

Werther (50), PBchard (30),

Melikoff and Pissarjewsky (26), and Pissarjewsky (32) have pointed out more or less clearly that the colored products obtained by adding hydro- gen peroxide to acidified chromic acid, vanadic acid, molybdic acid, and tungstic acid do not correspond to higher oxidation stages of these metals. Schwarz and Giese (43) say t.hat it is very improbable that chromium, which is in the sixth group, should ever have a valence of seven. Also, in all the other cases in which hydrogen peroxide reacts with an acid radical containing a metal, peroxide compounds are formed with an -0: 0- group and no increase in the valence of the central atom (pertitanate (2), perzirconate, pervanadate (27), perphosphate, etc.). They come to the conclusion that the so-called perchromic acid is not an acid at all, but a

There is nothing really new about this.







peroxide of the composition Cr05 and the formula


Over fifty years ago Moissan (28) wrote the formula CrOo.H202,which is still good. Since hydrogen peroxide reduces quadrivalent lead to bivalent lead in acid solutions and reverses this reaction in alkaline solutions, there must be a transition at some point which will not necessarily come at pH = 7. Schonbein (37) fixed the point between lead acetate and basic lead ace- tate. Zotier (52) confirmed this. With neutral lead acetate and hydro- gen peroxide he got no lead peroxide; with basic salts he got a slight forma- tion of lead peroxide; and with alkaline solutions he got plenty of lead peroxide. It is not certain just what is meant by basic lead acetate, so we have checked Zotier's results. Addition of hydrogen peroxide to a solution of lead acetate and lead monoxide in the proportions necessary to form Pbz(CH3C00)30H caused precipitation of lead peroxide. Addition of increasing amounts of 0.766 N potassium hydroxide to 5 cc. of a solu- tion of lead acetate (50 g. of (CH3C00)2Pb.3Hz0) in 100 cc. of water followed by addition of 5 cc. of a 30 per cent hydrogen peroxide gave the following results. With 1 cc. of potassium hydroxide no lead peroxide. The pH of the solution, as determined by the indicator method, was 6.5. With 2 cc. of potassium hydroxide there was formed lead peroxide. The pH of this solution was 7.0. The zero point for lead acetate to lead peroxide in the presence of potassium hydroxide is between pH 6.5 and 7.0. Substitution of sodium hydroxide does not affect the zero point within these limits of accuracy. Addition of increasing amounts of N/100 acetic acid to 5 cc. of a basic lead acetate solution (10 g. of basic lead acetate, Pbz(CH3COO),+.OH,in 100 cc. of water), followed by addition of 5 cc. of 30 per cent hydrogen peroxide gave the following results. With 35 cc. of acetic acid lead perox- ide was still formed, but 40 cc. of acetic acid prevented its formation. The pH values of these solutions were 7.0 and 6.4, respectively. When N/100 hydrochloric acid was added, 35 cc. did not prevent the formation of lead peroxide while 40 cc. did. This corresponds to pH values of 6.2 and 5.8, distinctly smaller than the 7.0 and 6.5 found with caustic alkali

and acetic acid.

have been proved by experiments in which a 1 per cent solution of po- tassium chloride was substituted more or less completely for the hydro- chloric acid. The results in table 3 were obtained for the varying amounts

This may have been a chloride effect.

This seems to






of potassium chloride necessary to prevent the formation of lead peroxide. When only potassium chloride was added to the basic lead acetate, the decrease in pH must have been apparent and not real. The basic lead acetate gives lead peroxide at a platinum anode. Schonbein (40) reports that hydrogen peroxide reduces alkaline cupric oxide to cuprous oxide, and Brodie (6) says that sodium peroxide oxidizes ammoniacal cupric chloride temporarily to a higher oxide. Both are wrong. Schonbein mistook the yellow of the so-called copper peroxide for the yellow of cuprous oxide. Parnell (29) made the same mistake about ten years later. Brodie did not realize that the so-called copper peroxide is really just that. It does not represent a higher valence for copper, any more than the so-called perchromic acid represents a higher valence of chromium. Cuprous salts are oxidized to cupric salts by hydrogen peroxide both in acid and alkaline solutions just as ferrous salts are oxidized to ferric salts.


Potassium chloride necessary to prevent the formation of lead peroxide





















Curiously enough a somewhat similar mistake has been made with regard to mercuric oxide. Martinon (25) says that mercuric oxide is re- duced to black mercurous oxide in alkaline solution by hydrogen peroxide. The electromotive force measurements for Hg IHgO and Pt I HgO con- tradict this. When pure mercuric oxide is treated with hydrogen peroxide in alkaline solution, it turns black as Martinon says, but the product is not mercurous oxide. By working at 0°C. as Pellini (31) did, one can isolate the red mercury peroxide, which is formed metathetically and

which gives a blue solution with chromic acid. On addition of alkali there is an evolution of oxygen and the red compound turns black. That is impure metallic mercury. If it is dissolved in dilute nitric acid, one can then precipitate mercurous chloride, but this is no evidence for the prior existence of mercurous oxide. It is not really surprising that one cannot measure the true electro-


There are other cases

can see the evolution of oxygen as a danger signal.

motive forces of hydrogen peroxide in acid and in alkaline solutions.

where one does not measure the true electromotive forces. Ozone is a stronger oxidizing agent than cobaltic sulfate, but electromotive force






measurements do not show it. Luther (24) has given a long list of criteria which should be met before one can postulate that a given electromotive

force connotes a given reaction. We do not care for the stipulation that the Peters equation is a necessary criterion. That way leads to the activity concept. Loimaranta (23) cites the cases of trivalent and pentavalent arsenic and trivalent and hexavalent chromic acid where iodine serves profitably as electromotive promoter. Of especial interest to us is the work of Forbes and Bartlett (9), who found that the apparent electromotive force of acidified chromic acid was raised considerably by addition of ammonium ferrous sulfate. We have confirmed this. With molar chromic acid in molar sulfuric acid an appar- ent value was obtained of E, = +0.990volt as given in table 1. On addition of ammonium ferrous sulfate this rose to E, = +1.150 or EI, = +1.45 volts. Chromous sulfate, stannous chloride, arsenious acid, and potassium ferrocyanide produce similar though smaller effects. Forbes and Bartlett at first considered this to be due to a change in the platinum electrode, but pointed out that the effect cannot be obtained with sulfurous acid or with hydrazine. No satisfactory explanation for this phenomenon has yet been given. Luther (24) obtained a rise of electromotive force by reducing an oxidiz- ing agent instead of oxidizing a reducing agent. A dilute chloric acid has almost no effect on hydrobromic acid. If reduced to chlorine dioxide by means of tetravalent vanadium, the chlorine dioxide oxidizes hydrobromic acid practically instantaneously. In molar sulfuric acid the apparent electromotive force of hydrogen peroxide increases somewhat with increasing concentration of hydrogen peroxide, whereas the true electromotive force must decrease. The following general conclusions can be drawn:

1. When the true electromotive force of any oxidizing or reducing agent,

with reference to any electrode and in any solution, is larger than the true electromotive force of hydrogen peroxide in the same solution, that sub- stance will be reduced by hydrogen peroxide, provided such a reaction is possible. If the true electromotive force is smaller than the true value for hydrogen peroxide, that substance will be oxidized by hydrogen peroxide, provided such a reaction is possible.

2. The true electromotive force, relatively to the hydrogen electrode,

of hydrogen peroxide in M hydrochloric or sulfuric acid is about +1.16 50.03 volts; the corresponding value in M potassium hydroxide is about +0.30 50.02 volt, subject to a correction for diffusion potential. The

zero points for iodine to iodic acid in M sulfuric acid and for hydrobromic acid to bromine are a,pparently Eh = +1.16 volts.

3. The primary reaction in the oxyhydrogen gas cell is the formation of

hydrogen peroxide, as postulated years ago by G. N. Lewis and by Haber.

4. The oxygen anion in hydrogen peroxide is Ol, as shown hy Tanatar.








5. The current-voltage curve for a sodium peroxide solution between

platinum electrodes is the same type as that for a copper sulfate solution between copper electrodes.

6. Hydrogen peroxide may be considered as dissociating reversibly into

2H + 0.0. Reduction is done by the two hydrogen atoms and oxida- tion by the 0.0. The symmetrical structure for hydrogen peroxide is indicated. 7. In the reaction between hydrogen peroxide and lead peroxide in acid solution, the lead peroxide is reduced by the hydrogen from the hydrogen peroxide, and all the oxygen gas comes from the hydrogen peroxide. This

is the view put forward by Weltzien, Traube, and Baeyer.

8. In the catalytic decomposition of hydrogen peroxide the reaction is

2H + 0.0 + H202 + 2H20 + 02

and not

H202 4

HZ0 + 0

In the presence of platinum the

This is the view advocated by Wieland. reactions may be written

H202 + Pt = Pt(2H) + 02


H202 + Pt(2H) = Pt + 2H20

The measured reaction is therefore monomolecular. 9. Bray should have said that we get an oxidation-reduction catalysis

of hydrogen peroxide when one electromotive force is larger than Eh = +l.l6 volts and one is smaller. He was led astray by Haber’s hypothesis

of an oxidation value for hydrogen peroxide greater

10. The blue so-called perchromic acid does not contain chromium with

a higher valence than six.

The so-

called pertungstates, pertantalates, pervanadates, permolybdates, perti- tanates, perzirconates, peruranates, perborates, etc., do not contain higher

oxides; nor do copper peroxide and mercury peroxide. Acid permanganate

is reduced by the blue compound just as it is by hydrogen peroxide. is not reduced by chromic acid.


than Eh = + 1.16 volts.

This is the view upheld by Moissan.

11. When a substance is reduced by hydrogen peroxide in strongly acid

solution and oxidized in a strongly alkaline solution, or the other way around, there must be an intermediate pH at which neither change takes

place for any given concentration of hydrogen peroxide. With lead ace-

Presence of chloride

tate this point comes between pH = 6.5 and 7.0. displaces the apparent position of the point.

12. No satisfactory explanation has yet been given for the rise of







electromotive force when ammonium ferrous sulfate, chromous sulfate,

stannous chloride, arsenious acid, or potassium ferrocyanide is added to an acidified chromic acid solution.

13. In molar sulfuric acid the apparent electromotive force of hydrogen

peroxide increases with increasing concentration of hydrogen peroxide,

whereas the true electromotive force must decrease.

14. Hydrogen peroxide reduces acidified potassium iodate to iodine when

the pH is larger than about 1.2 to 1.4, and oxidizes iodine to iodic acid when the pH is smaller than that.

15. In approximately molar caustic potash, hydrogen peroxide should

apparently oxidize potassium iodide to iodate, but the first step in such an oxidation is the formation of potassium hypoiodite and this substance is reduced by hydrogen peroxide. Consequently both potassium iodide and potassium iodate are practically stable to hydrogen peroxide in alka- line solutions.

16. To oxidize alkaline potassium iodide to iodate, one must use a more

powerful oxidizing agent than potassium hypoiodite. Ozone and alka-

line permanganate meet this requirement.

17. It is now possible to draw a sharp dividing line between peroxides

and dioxides. The term lead peroxide is so well established that it is doubtful whether a change in nomenclature is wise.

18. The chemistry of hydrogen peroxide is a hopeless subject for the

phenomenological, or Baconian, experimenter, because the misleading ex-

periment is everywhere.


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