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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
a t about Et, = +0.8 volt and an oxidizing potential a t about E h = +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 a t about EJ, = $0.8 volt and
about E h = +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-
cal. Bray ( 5 ) gives Eh = +1.78 volts.
The real relation is quite simple. 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
OXIDATION AND REDUCTION WITH HYDROGEN PEROXIDE 379
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 a t 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 E h 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.
To many people this will seem a deplorable state of affairs. They will
feel that we should have corrected all these data and that we should have
given our data a t 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 a t 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
380 WILDER D. BANCROFT AND NELSON F. MURPHY
REACTION REACTION
ipproxi- E, Approxi EC
nate E A (Murphy) mate El Mwhy)
-- -
KMnO4-K2MnO~ +O ,73 +O .43 PbO+PbOz +O. 27 -0.030
KzFeOa-+Fe~Oa $0.71 +O .41 KItKIOa* +O .16 -0,145
NaClO-+NaCl* +0.70 $0.40 Hg-HgO +0.15 -0.15
KzMnO4+MnO2 $0.59 +O ,294 KCN-KCNO +O. 13 -0.175
AgzOz?+AgzO +O .58 NazSOs+NazSO4* +O.ll -0.19
Bi20j-tBi~0~ $0.58 +O. 279 BizOs-+BizOa $0.11 -0.19
Ferricyanide-ferro- +O .51 +O ,214 MnO+Mn02 +o. 11 -0.19
cyanide coo-.cozos +o. 10 -0.20
Ni203-Ni0 +O .51 +O. 21 Cr~03-tK~CrO4* +O .08 -0.22
KIOI+KIO +0.44 TlzO+TlzOs +0.05
AgzOAAg +0.34 +O ,038 KNOz-+KNOs f0.01
cuzo-tcuo -0.08
NHzOH-+Nz* -0.29 -0.59
Pb+PbO -0.56
FeO-tFezOs -0.83
SnO+SnOz -0.87
Zn--+IYa~ZnO~ -1.11)
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 a t some point which will not necessarily come a t 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. This may have been a chloride effect. This seems to
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
OXIDATION AND REDUCTION WITH HYDROGEN PEROXIDE 393
cc. cc.
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 a t 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.
I n 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 5 0 . 0 2 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 O l , as shown hy Tanatar.
OXIDATION AND REDUCTION WITH HYDROGEN PEROXIDE 395
and not
H202 4 HZ0 +0
This is the view advocated by Wieland. In the presence of platinum the
reactions may be written
H202 + Pt = Pt(2H) + 0 2
and
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 . l 6 volts and one is smaller. He was led astray by Haber’s hypothesis
+
of an oxidation value for hydrogen peroxide greater than Eh = 1.16 volts.
10. The blue so-called perchromic acid does not contain chromium with
a higher valence than six. This is the view upheld by Moissan. 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. It
is not reduced by chromic acid.
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 a t which neither change takes
place for any given concentration of hydrogen peroxide. With lead ace-
tate this point comes between pH = 6.5 and 7.0. Presence of chloride
displaces the apparent position of the point.
12. No satisfactory explanation has yet been given for the rise of
396 WILDER D. BANCROFT AND NELSON F. MURPHY