The thermal decomposition of hydrogen peroxide vapour

B y R obert C. M a c k e n z ie and M o w b r a y R it c h ie

( Communicatedby .J Kendall,

The decomposition of hydrogen peroxide vapour at pressures less than 1 mm. in silica
vessels has been investigated, mainly at 80° C, but also over the temperature range 15-140° C.
Oxygen at low pressures was found to have no appreciable influence on the rate of decom­
position; water vapour retarded the rate slightly. The reaction was predominantly a surface
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one. In one vessel, the decomposition was bimolecular with respect to the peroxide pressure,
the rate being given by fc[H20 2]2/(l + 6[H 20 ])2: in another, the bimolecular reaction of the
final stages at low peroxide pressures was preceded by one of order approximately 0*7 at the
high pressures.
Higher pressures of oxygen and nitrogen retarded the decomposition appreciably. At
higher pressures of water vapour, a pronounced periodicity in rate was evident.
The apparent heat of activation over the temperature range investigated was not constant,
being calculated as 4200 cal. from rates at 15 and 70° C and 8400 cal. from rates at 80 and
140° C. On the assumption that the lower value more nearly represents the surface reaction,
the velocity of decomposition, calculated for 1 mm. pressure of peroxide at 50° C by the
theory of absolute reaction rates, was 0*70 x 1013 mol.cm .”2 sec.”1, in agreement with the
experimental value of 0-76 x 1013 mol.cm .”2 sec.”1.

While the thermal decomposition of hydrogen peroxide in solution has been in­
vestigated by many workers, as far as has been ascertained only three communica­
tions have appeared which deal with the corresponding decomposition in the vapour
phase. All three support the conclusion th a t the reaction is heterogeneous, the rate
being markedly influenced by the nature of the containing surfaces. Hinshelwood &
Prichard (1923) found the reaction to be unimolecular on glass, but the rates of
Elder & Rideal (1927), non-reproducible on glass, were, on quartz, best expressed as
a zero-order reaction inhibited by the product oxygen. Elder & Rideal found th a t
a t 85° C the rate of decomposition became zero when approximately 20 % of the
peroxide initially present had decomposed; to obtain an ‘infinity’ pressure reading
corresponding to complete decomposition, it was necessary to heat to a considerably
higher temperature. Kistiakowsky & Rosenberg (1937) reported, however, no
cessation of reaction short of complete decomposition on a quartz surface, and no
inhibition by oxygen was observed.
Hydrogen peroxide is regarded as an intermediate of importance in several
reactions which involve hydrogen and oxygen (e.g. the thermal combination of
hydrogen and oxygen, the photosynthesis of hydrogen chloride in the presence of
oxygen), where the mechanisms proposed depend partly on the behaviour of the
peroxide present. In such systems the amount of peroxide is usually very small.
In view of the apparent lack of agreement concerning the heterogeneous decom­
position, and the possible application to these other reactions, the thermal decom­
position of peroxide vapour a t relatively low pressures (less than 1 mm.) has here
been investigated for silica vessels.

Vol. 185. A. [ 207 ] 14

 208 R. C. Mackenzie and M. Ritchie

E xperimental procedure
Preparation of peroxide
The hydrogen peroxide employed was obtained from sodium peroxide and dilute
sulphuric acid by distillation methods based on th a t of Kilpatrick, Reiff & Rice
(1926).
A final fraction of some 6-8 c.c., of 80 % purity or over, was finally concentrated
by further distillation in vacuo, with connexion to a concentrated sulphuric acid
bulb D as shown in figure 1. In this way concentrations of peroxide up to 100 %
could be obtained, the final volume of liquid being usually from 1 to 2 c.c. The
product was normally kept solid by a carbon dioxide-ether freezing mixture.
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The molar percentage of peroxide in such preparations was determined by titra ­

tion with potassium permanganate solution, previously standardized by sodium
oxalate. For the more concentrated solutions a special pipette was employed,
‘aged ’ by previous contact with the solution so th a t no appreciable decomposition
occurred during the transference of the sample to a weighed amount of water in a
tared vessel. Immediate reweighing and titration followed. The final fractions
distilling over had a tendency to collect in droplets on intervening cold surfaces, but
the most concentrated liquid did not appear to be much more viscous than water,
in accordance with the measured viscosities of Maass & Hatcher (1920). The most
concentrated samples appeared quite stable in the receiver in which they were
collected by distillation, but, if transferred to another vessel, decomposition at once
commenced, as shown by the appearance of gas bubbles originating at the walls of
the vessel. On evacuation by oil pump, samples of approximately 99 % purity
showed little gas evolution, but at 95 % or less such decomposition was more in
evidence. On reducing the temperature of 99 % samples to —80° C, the liquid froze
readily; with 90-95% samples no crystallization occurred unless the vessel was
tapped or disturbed, when solidification took place immediately. For concentra­
tions less than 95 %, such solidification became increasingly difficult, in agreement
with the observations of Maass & Herzberg (1920). No explosive tendency was
observed during any of the above-described manipulations.

The thermal decomposition

The apparatus employed is shown in figure 1, and was constructed entirely of
soda-glass with the exception of the transparent silica reaction vessel Apiezon
grease L was used on such taps and ground joints as were unavoidable. Receiver C
contained the peroxide, normally kept solid at —80° C; on melting, vapour was
introduced to the vessel V via the tap Tz and the capillary tubing with the ground
joint J , its pressure being recorded by the Bourdon spring gauge G, movement of
the pointer of which was observed against the eyepiece scale of a telescope. The
gauge was calibrated by means of dry air, at pressures recorded by the standard
mercury manometers Mx and M2. These manometers also served for measurement of
 Thermal decomposition of hydrogen peroxide vapour 209
pressures of other gases introduced into the reaction vessel, when the pressures
employed were in excess of those which could be read directly from the gauge. The
gauge itself was water-jacketed a t 26° C, the temperature remaining constant within
0*1° C for any one run. Except in the series of experiments on temperature variation,
the reaction vessel was immersed in a covered water therm ostat a t 80° C, again with
variation of less than ± 0-1° C. For higher temperatures, an electrically heated
furnace system was used, the temperature being controlled by a hand rheostat to
within 0*3° C.
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Oxygen, nitrogen, hydrogen and carbon dioxide were obtained from cylinders, and
after suitable purification were stored in glass bulbs attached to the apparatus. The
reservoir E contained the purest distilled water obtainable, suitably boiled out
under reduced pressure in the apparatus itself.
In an experimental decomposition, the entire system was first evacuated by oil
pump, the vessel and gauge being subjected alone to further evacuation for 45 min.,
during which time the freezing mixture was removed from the reservoir C. Tap Tb
to the concentrated sulphuric acid container D was opened immediately the peroxide
became liquid, this tending to remove any water vapour formed by decomposition.
Taps T3and jT4 were then closed and tap Tx opened to remove any accumulated
oxygen from the reservoir. When after a few minutes all gas had been removed, taps
Ts and T6 were closed, the zero reading of the gauge noted and tap Tz to the vessel
and gauge opened. The movement of the pointer was observed, and when the
required pressure had been reached, taps Tx and were closed, the gauge reading
observed and the time noted. Pressure readings were then taken at frequent
intervals. The ‘infinity’ reading corresponding to complete decomposition was
observed after several hours, usually overnight. On re-evacuation, the zero reading
of the gauge was rechecked.
The above procedure was suitable for the introduction of vapour up to 1 mm.
pressure, which is approximately the maximum vapour pressure of 98 % molar
peroxide at room temperature (Maass & Hiebert 1924). When other gases required
to be added to much higher pressures, any water or peroxide vapour was removed
 210 R. C. Mackenzie and M. Ritchie
from the connecting tubing by oil-pump evacuation for 1 | min., and the second gas
introduced slowly into the reaction vessel, the pressure in the gauge jacket being
allowed to increase simultaneously so th at the gauge pointer remained more or less
in the zero position. The pressure of added gas was then calculated from the mercury
manometer readings. The time taken to perform the entire operation varied with
the amount of gas introduced but was normally 4-7 m in.: thereafter pressure changes
in the reaction vessel were recorded as above. In view of the small volume of the
connecting capillary tubing, no correction was considered necessary for the vapour
swept back into the vessel on the secondary introduction of gas. The volumes of the
reaction vessels used were 31-35 and 21-75 ml; special experiment showed th a t any
decomposition occurring in the connecting tubing and gauge could have only a
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negligible effect on the pressure change observed during a normal determination.

W ith daily experiment, in which a 96% sample was melted and refrozen as
required, the final concentration at the end of 3 weeks was 94 %; the preservation
of the sample by the methods described was thus effective.
Three Bourdon gauges were used in all, the sensitivity in each case being found
to be independent of the pressures in the reaction vessel. The actual sensitivities
were 23-0, 27-0 and 54-1 telescope scale divisions per millimetre: it was found possible
to read such scale division to the nearest tenth of a division, which gave the smallest
observable pressure change as approximately 0-004, 0-004 and 0-002 mm. respec­
tively. In all decompositions a smooth curve was drawn through the points obtained
by plotting pressure against time, and from this curve pressures could be determined
fairly accurately to the nearest 0-002 mm.

R esults and discussion

I t should be stated th a t in the first runs carried out with the large reaction vessel
no increase in pressure was observed even after several hours. After several attem pts,
however, increases in pressure became apparent, and after several more became
satisfactorily reproducible. W ith the smaller vessel, the first few results were again
erratic, but again on repetition reproducible results were attained. Regreasing of
taps did not normally produce appreciable irregularities; the initial results are
regarded as symptomatic of the ‘ageing ’ of the silica surfaces. Apparently irregular
results were sometimes obtained during the various series, these being largely due to
decomposition of the vapour during introduction to the reaction vessel, as appeared
when the ‘infinity ’ pressures were examined.
The normal equation for the decomposition of hydrogen peroxide indicates th a t
2 vol. peroxide vapour should give rise to 2 vol. water vapour and 1 vol. oxygen. In
relation to the initial pressure of peroxide, the pressure should therefore increase by
50 %, on the assumption th a t no condensation and no adsorption of reactant or
products takes place. At the pressures involved condensation may be disregarded.
The composition of the liquid in the reservoir being known, use was first made of the
results of Giguere & Maass (1940) to give the composition of the vapour over the
 Thermal decomposition of hydrogen peroxide vapour 211
liquid. If no adsorption phenomena were in evidence and if no appreciable decom­
position occurred during the experimental manipulation involved, then the observed
pressure increase should correspond to the calculated vapour pressure above the
liquid. Two sets of experiments were performed. In the first, the normal determina­
tion, a known pressure of vapour was introduced to the reaction vessel a t a fixed
tem perature and the decomposition allowed to proceed to completion, when the
final pressure was recorded. In the second a small tube containing phosphorus
pentoxide was temporarily sealed to the system (adjacent to the ground joint J),
with a view to absorbing all the water formed; in this case the final pressure (of
oxygen) ought to be one-half of th a t of the peroxide originally introduced.
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In carrying out such experiments one complication became evident. Immediately

after the introduction of vapour to the vessel, the pressure decreased slightly before
the normal increase due to decomposition ensued. This decrease, normally small and
of short duration, is discussed below. The procedure adopted was to extrapolate the
smooth decomposition curve back to zero time, the resultant pressure value being
used in the calculations. In table 1, p 0 is the initial pressure observed immediately
on closing the entry tap to the vessel, p'0 the extrapolated initial pressure and p ^
the ‘infinity’ pressure. The initial molar percentage of peroxide in the vapour is
given as [H20 2]m.
Table 1
V essel volu m e = 31*35 m l. Tem p. = 82*0° C.
Molar concentration o f H 20 2 in th e solution = 78*4 %.
Molar concentration o f H 20 2 in vapour (according to Giguere and Maass) = 39*0 %.
norm al determ ination P 20 5 determ ination

Po Po Poo [H 2Oa]m Po Poo [H 20 2],

mm. mm. mm. % mm. mm. %
1*18 1*15 1*37 38 0*93 0*20 43
0*97 0*94 1*23 37 0*90 0*16 36
0*96 0*91 1*07 35 0*75 0*15 40
0*92 0*89 1*06 38 0*01 0*12 39
m ean = 37 m ean = 39*5

In view of the relatively small difference between the experimental values and
those of Giguere & Maass, it was concluded th at the manipulation involved does lead
to the introduction of vapour to the reaction vessel, of essentially the same com­
position as th at above the solution, and th a t for such conditions the pressure changes
may be used to follow the rate of decomposition. As shown above, however, the
initial adsorption though small is not inappreciable, and it is advisable to consider
it in more detail.
The actual shape of the experimental pressure-time curve in its initial stages will
be determined by two main factors, the decrease due to adsorption and the increase
due to decomposition. In general such adsorption must be attributed to both
peroxide and water, but the amount of peroxide adsorbed will, after adsorption
 212 R. C. Mackenzie and M. Ritchie
equilibrium is attained, decrease as the concentration of peroxide in the gas phase
decreases on decomposition, while th a t of the water present will increase con­
tinuously as the product concentration increases. Results soon showed th a t the
decomposition was not a zero-order reaction;,the greater the relative amounts of
peroxide to water, the greater will be the initial rate of increase of pressure and the
closer the observed rate to the theoretical rate required.
W ith the purest peroxide obtainable, a small initial decrease could be detected
indicating adsorption of H 20 2 itself on the surface. This decrease was so small th at
the usual method of extrapolation gave a value very little different from the
initial p 0.The experimental initial rates in this case must be very close to the ‘ideal
values. When, however, the final p ^pressures are considered,
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measured Pa, would be slightly greater than the ‘ideal’ value, referred to p ’^, because
of the complete decomposition of the initially adsorbed layer, if all the water formed
during the course of the reaction were to remain unabsorbed in the vapour phase.
The adsorption of water which must be assumed to take place will tend to give a
lower Pa,; the actual value recorded will depend on these two opposing tendencies.
Experiment showed th a t the purest peroxide obtainable (99-8-100-0 %) as found by
permanganate analysis, when introduced to the reaction vessel at 0-3 mm. pressure
gave at 80° C apparent percentages of slightly over 100, viz. 101-0, 101-5. Here
again only a small error is involved in the extrapolation method in spite of the
adsorption possibilities.
In general, the vapour used in the majority of the decomposition experiments
contained, initially, varying amounts of water. Even in the case of the dilute (39 %)
vapour of table 1, however, the initial decrease was observed only for 2 or 3 min.
in a decomposition requiring over 100 min. The observed rates will here be lower
than the true rates, even with the extrapolation, but after the initial stages, the
rate will approximate closely to the true rate, because the wrater forifled will not alter
appreciably the relatively large concentration of water already present. The infinity
value as already shown in table 1 is somewhat low. On the other hand, pure peroxide
will show a closer approach to the true initial rate values, but the infinity value will
be somewhat high. By selecting an initial concentration between these two extremes,
the initial rates might be expected to be on the low side, but the later rates and the
infinity values ought to be sensibly correct. In practice, an 85 % vapour (from 96 %
liquid) gave an initial decrease of 0-01 mm. for a final pressure change —p'0 of
0-45 mm.; in view of the smallness of the adsorption effect, it is believed th a t the
rates as obtained by the short extrapolation are not appreciably in error.

Variation of pressure of oxygen

Since the results of Elder & Rideal were best expressed by an equation involving
inhibition by oxygen, rates were determined for a certain initial peroxide con­
centration with and without the addition of 8-3 mm. oxygen, this amount being
much larger than the amount of oxygen produced during the decomposition. Results
are given in table 2, where P is the total pressure.
 Thermal decomposition of hydrogen peroxide vapour 213

T able 2

V essel volu m e = 31*35 m l. Tem p. = 82*2° C. [H 20 2]ra = 80 %.

experim ental valu es values from sm oothed curve

t P t P [H 20 2] [H 20 ]
m in. mm. m in. mm. m m. mm.
(a) initial [0 2] = 0*0 m m .
0 0*693 0 0*693 0*554 0*139
5 0*711 5 0*716 0*508 0*185
10 0*737 10 0*738 0*464 0*229
15 0*759 15 0*759 0*422 0*271
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20 0*778 20 0*778 0*384 0*309

25 0*793 25 0*794 0*352 0*341
30 0*808 30 0*809 0*322 0*371
40 0*830 40 0*831 0*278 0*415
51 0*848 50 0*848 0*244 0*449
62 0*867 60 0*862 0*216 0*477
(6 ) initial [ 0 2] = 8*3 m m .
0 0*689 0 0*689 0*550 0*139
4 0*711 5 0*712 0*504 0*185
10 0*734 10 0*734 0*460 0*229
16 0*756 15 0*755 0*418 0*271
20 0*774 20 0*774 0*380 0*309
25 0*789 25 0*790 0*348 0*341
30 0*804 30 0*805 0*318 0*371
40 0*822 40 0*827 0*274 0*415
53 0*845 50 0*843 0*242 0*447
77 0*874 60 0*857 0*214 0*475
88 0*882

Comparison of the concentrations attained after the various time periods shows
th a t the added oxygen had no effect on the rate of decomposition for these con­
ditions. The small amount of oxygen gas here produced during a run therefore does
not require to be considered in the expression for the rate of reaction.

Variation of pressure of hydrogen peroxide

I t was desired to measure the rates at different pressure of peroxide, while other
factors, including the pressure of water vapour, remained constant. Experiments
were performed with initial total pressures ranging from 0*6 to 1*2 mm., which gave
an approximate 3:1 variation in pressure of peroxide for the pressure of water
vapour chosen. Rates were determined from the pressure-time curves for this water
vapour value; these are considered accurate to approximately 0*0005 mm./min.
Results are given in table 3.
As shown by column 5, the rate is proportional to the square of the peroxide
concentration here concerned. The calculated rates were obtained from the equation
j?Caic = 0*055[H2O2]2; the ratios of the final column show th at the variation of rate
with [H20 2] concentration is adequately represented in this way.
 214 R. C. Mackenzie and M. Ritchie

T able 3
V essel volu m e = 31-35 m l. Tem p. = 82-0° C. P artial pressure o f w ater vapour = 0-350 m m .

p'o [H 2o 2]TO [H 20 2] rate

mm. % mm. m m ./m in. i* /[H 20 2P -^calc ^ ca lc^ ex p
1-150 82 0-800 0-0350 0-055 0-0352 0-99
1-140 70 0-790 0-0350 0-056 0-0343 1-02
1-050 68 0-700 0-0265 0-054 0-0270 0-98
0-785 84 0-435 0-0102 0-055 0-0102 1-00
0-741 84 0-391 0-0088 0-058 0-0084 1-05
0-740 80 0-390 0-0085 0-056 0-0084 1-01
0-650 77 0-300 0-0052 0-058 0-0050 1-04
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Variation of pressure of water vapour

Experiments were carried out, first with no added water vapour and then with
approximately 1, 3, 5 and 10 mm. added vapour. Rates were determined a t a con­
stant pressure of hydrogen peroxide. The results, with the exception of the 10 mm.
run which was abnormal and will be discussed later (p. 220), are given in table 4.

T able 4
V essel volu m e = 31-35 m l. Pressure o f H 20 2 = 0-400 m m .

tem p. [H aO] -^exp ^calc

°C mm. m m ./m in. m m ./m in. ^calc
82-1 0-284 0-0085 0-0086 1-01
82-2 1-281 0-0065 0-0066 1-01
82-2 3-289 0-0047 0-0042 0-89
81-7 5-289 0-0029 0-0029 1-00

The higher the concentration of water vapour, the lower is the rate; calculated
rates were obtained from the expression

^caic = 0-0094/(1 + 0-15[H2O])2.

The ratios of the last column show th a t the retarding effect of water vapour is
satisfactorily expressed in this way.

Thegeneral rate equation

The above dependence of rate on the pressures of peroxide and water may be
combined in the form

«c.io = - | [ H , 0 , ] = 0-060[H20 2]S/(1 + 0-15[H2O])s,

where the units are millimetres and minutes. This equation was then applied to
several complete decompositions throughout their course. The results are given in
table 5.
 Thermal decomposition of hydrogen peroxide vapour 215
The agreement between the calculated and experimental rates in all cases is
satisfactory, and there seems no doubt th a t the equation applied does represent the
rate of decomposition for the conditions in question. The experimental rates in the
initial stages are somewhat lower as a rule than the calculated rates, in agreement
with the previous considerations of adsorption. The fluctuations observed near the
completion of a decomposition are no doubt due to the difficulty of accurately
determining the rate of the very slow reaction in these final stages.
For water-vapour pressures less than 1 mm., the denominator (1 + 0-15[H2O])2
may be replaced by (1 + 0*30[H2O]) without loss of accuracy; velocity coefficients
may then be obtained for such conditions as follows.
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Let a be the original amount of reactant H 20 2 a t time 0, the amount trans­

formed a t time t (i.e. the amount of water formed), and c the amount of water
initially present a t t = 0.
dx k—
Then — -- = - ——.
dt 1 + b(c + x)
n ., ,. 7 1 x{l + &(c + a)} a
On mtegration k= - 7 - ------ —— log-------- .
t (a —x)a t a —x
A straight line should then be obtained by plotting x/t(a —x) against
l/t —loga/(a —x);
the slope of the line will be ab/{l+b(c + a)}, and the intercept on the x/t(a —x) axis
will be ka/{1 + 6(c + a)}. From these values k and b can be calculated for th at experi­
ment. This method for the pressures in question is somewhat sensitive to experi­
mental error. In the following table 6, k has been calculated from the integrated
equation by taking b = 0-30 for one experiment.
The variations in k thus obtained are well within the experimental error, as was
shown by choosing arbitrary values of x and calculating for k = 0*0556 and b = 0*30
concentrations and total pressures a t the corresponding times throughout the run.
The curve obtained by plotting these calculated total pressures against time was
practically identical with the experimental curve.
Theoretically the general rate equation above is applicable to a bimolecular
surface reaction retarded by one of the products, and can be derived in the usual
way by assuming a weakly adsorbed reactant and a more strongly adsorbed product,
the rate being proportional to the square of the amount of reactant on the uncovered
surface. Although such a type of reaction has been predicted theoretically, as far
as has been ascertained, no exactly similar reaction has been reported. The thermal
decomposition of nitric oxide on platinum (Bachman & Taylor 1929), strongly
retarded by oxygen, has been expressed by the equation
dx k(a—
dt x
here the theoretical term (1 + bx)2h as presumably approxim
reason of the very strong adsorption of oxygen under the experimental conditions.
 216 R. C. Mackenzie and M. Ritchie
I t might be expected th at at higher pressures of peroxide, with greater saturation
of the surface, a zero-order reaction might become predominant; this is then in
agreement with the results of Elder & Rideal, where, however, it would now appear
that water and not oxygen is the main retarding product. The question of much

T able 5
V essel volum e = 31*35 m l.
t p [H 20 2] [H 20 ]
m in. mm. m m. m m. -^exp -^cale P calc/-®exp
(a) initial [H 20 2‘\m = 68-0 %; tem p. = 80-0° C
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0 1-050 0-715 0-335

5 MOO 0-615 0-435 0-0175 0-0201 1-15
10 1-140 0-535 0-515 0-0136 0-0148 1-09
15 1-170 0-475 0-575 0-0115 0-0116 1-01
20 1-196 0-423 0-627 0-0090 0-0090 1-00
25 1-215 0-385 0-665 0-0073 0-0074 1-01
30 1-230 0-355 0-695 0-0064 0-0063 0-98
40 1-255 0-305 0-745 0-0046 0-0046 1-00
50 1-275 0-265 0-785 0-0034 0-0034 1-00
60 1-290 0-235 0-815 0-0027 0-0027 1-00
80 1-311 0-193 0-857 0-0018 0-0018 1-00
100 1-322 0-171 0-879 0-0011 0-0014 1-27
160 1-349 0-117 0-933 0-0008 0-0006 0-75

(b) initial [H 20 2];m = 80-0 %; tem p. = 80-0° C

0 0-740 0-590 0-150
5 0-780 0-510 0-230 0-0140 0-0146 1-04
10 0-810 0-450 0-290 0-0114 0-0112 0-98
15 0-835 0-400 0-340 0-0088 0-0088 1-00
20 0-854 0-362 0-378 0-0070 0-0071 1-01
25 0-870 0-330 0-410 0-0060 0-0058 0-97
30 0-884 0-302 0-438 0-0048 0-0048 1-00
40 0-905 0-260 0-480 0-0036 0-0036 1-00
50 0-920 0-230 0-510 0-0027 0-0028 1-04
60 0-933 0-204 0-536 0-0022 0-0022 1-00
80 0-951 0-168 0-572 0-0014 0-0014 1-00
100 0-964 0-142 0-598 0-0009 0-0010 1*11

(c) initial [H 20 2]m = 84-0 %; tem p. = 81-3° C

0 0-741 0-622 0-119
5 0-781 0-542 0-199 0-0146 0-0167 1-14
10 0-815 0-474 0-267 0-0125 0-0125 1-00
15 0-843 0-418 0-323 0-0098 0-0096 0-98
20 0-863 0-378 0-363 0-0075 0-0077 1-03
25 0-878 0-348 0-393 0-0063 0-0065 1-03
30 0-890 0-324 0-417 0-0052 0-0056 1-08
40 0-912 0-280 0-461 0-0041 0-0041 1-00
50 0-930 0-244 0-497 0-0032 0-0031 0-97
60 0-944 0-216 0-525 0-0024 0-0024 1-00
80 0-963 0-178 0-563 0-0019 0-0016 1-07
100 0-974 0-156 0-585 0-0010 0-0012 1-20
 Thermal decomposition of hydrogen peroxide vapour 217
T able 5 ( continued)
(d) in itial [H 20 2]m = 77*0 %; tem p. = 81*5° C
0 0-650 0-500 0-150
5 0-682 0-436 0-214 0-0105 0-0107 1-02
10 0-705 0-390 0-260 0-0082 0-0085 1-04
15 0-725 0-350 0-300 0-0070 0-0068 0-97
20 0-741 0-318 0-332 0-0058 0-0055 0-95
25 0-754 0-292 0-358 0-0045 0-0046 1-02
30 0-766 0-268 0-382 0-0040 0-0039 0-98
40 0-785 0-230 0-420 0-0028 0-0028 1-00
50 0-800 0-200 0-450 0-0024 0-0021 0-88
60 0-811 0-178 0-472 0-0018 0-0017 0-94
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70 0-820 0-160 0-490 0-0014 0-0013 0-93

90 0-832 0-136 0-514 0-0010 0-0010 1-00
(e) initial [H 20 2]m = 84-0 %; tem p. = 81-5° C
0 0-367 0-308 0-059
5 0-382 0-278 0-089 0-0052 0-0045 0-87
10 0-393 0-256 0-111 0-0040 0-0038 0-95
15 0-402 0-238 0-129 0-0034 0-0033 0-97
20 0-410 0-222 0-145 0-0027 0-0028 1-04
30 0-424 0-194 0-173 0-0023 0-0021 0-91
40 0-436 0-170 0-197 0-0018 0-0016 0-89
50 0-445 0-152 0-215 0-0015 0-0013 0-87
60 0-452 0-138 0-229 0-0012 0-0011 0-92
( / ) in itial [H 20 2] m = 82-0 %; tem p. = 80-0° C
0 1-150 0-944 0-206
5 1-245 0-754 0-396 0-0290 0-0305 1-05
10 1-305 0-634 0-516 0-0198 0-0209 1-06
15 1-345 0-554 0-596 0-0148 0-0156 1-05
20 1-377 0-490 0-660 0-0118 0-0120 1-02
25 1-400 0-444 0-706 0-0097 0-0097 1-00
30 1-425 0-394 0-756 0-0078 0-0076 0-97
40 1-460 0-324 0-826 0-0055 0-0051 0-93
50 1-485 0-274 0-876 0-0040 0-0036 0-90
60 1-503 0-238 0-912 0-0028 0-0027 0-96
70 1-516 0-212 0-938 0-0022 0-0021 0-95
80 1-527 0-190 0-960 0-0018 0-0017 0-94

T able 6
V essel volum e = 31*35 m l. Temp. = 80*0° C. Initial pressure o f H 20 2 — a — 0*715 mm,
In itial to ta l pressure = c + a = 1*050 m m . In itial pressure o f H 20 = a = 0*335 m m.
t X a —x 1 X 1 a
kog
l k
m in. mm. mm. t (a —x) t a-x
20 0-292 0-423 0-0346 0-0263 0-0555
30 0-360 0-355 0-0337 0-0233 0-0550
40 0-410 0-305 0-0335 0-0213 0-0552
50 0-450 0-265 0-0340 0-0199 0-0566
60 0-480 0-235 0-0337 0-0185 0-0564
80 0-522 0-193 0-0337 0-0166 0-0570
100 0-544 0-171 0-0318 0-0143 0-0542
160 0-598 0-117 0-0319 0-0113 0-0553
m ean k = 0*0556
 218 R. C. Mackenzie and M. Ritchie
higher oxygen pressures is referred to later (p. 222). The observation of these workers
th a t reaction ceased after 20 % decomposition, a phenomenon not observed in any
of the present experiments, is perhaps to be explained on the assumption th a t the
large amount of water present so reduced the surface available for decomposition
at the temperature concerned th a t a measurable rate was not attained. Their initial
rates are some ten times less than th a t expected on the basis of the general equation,
applied per unit apparent surface of the containing vessel; this again is not in
disagreement with the above assumption.

Thetemperature coefficient and the absolute rate of reaction

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Several experiments were carried out over the tem perature range 15-137° C, the
rate at the higher tem perature being so rapid th a t any further accurate measurement
above this temperature became impossible for the concentrations and apparatus
employed. Reaction rates were determined as before a t a fixed partial pressure of
hydrogen peroxide. The pressures of water vapour present were not exactly the
same in each experiment, and the rates were accordingly corrected by applying the
general equation. Such corrections were, however, small in all cases. Results are
given in table 7, where the last column gives the rates corrected to [H20] = 0-745 mm.
I t is then apparent th a t the tem perature coefficient is in general small, but not
constant over the range considered. After conversion from millimetre units to
molecular concentrations for each temperature, the apparent heat of activation was
calculated in the usual way as 5500 cal. for the range 15-82° C and as 8400 cal. for
the range 82-137° C. I t is possible th a t a t the higher temperatures a gas-phase
reaction was becoming appreciable; if so, the apparent heat of activation for the
surface reaction will be somewhat less than the lower figure.

Table 7
V essel volu m e = 31-35 m l. [H 2Oz] = 0-320 m m .
tem p. -Oexp -^corr tem p. -^exp ^corr
°C m m ./m in. m m ./m in. °C m m ./m in. m m ./m in.
15 00013 0-0010 99 0-0095 0-0095
50 00027 0-0025 111 0-0115 0-0115
60 0-0020 0-0018 120 0-0146 0-0142
70 0-0030 0-0029 137 0-0210 0-0208
82 0-0050 0-0049

Evaluation was attem pted of an* equation deduced from the theory of absolute
reaction rates for a bimolecular surface reaction inhibited by one of the products, for
comparison with the rate as experimentally determined. The equation derived
theoretically for such a reaction is (Glasstone, Laidler & Eyring 1941, p. 385)

C»C. /,
2 (1 + A pGgp) h f , F* •
 Thermal decomposition of hydrogen peroxide vapour 219
where V = rate of reaction,
8 = total number of possible sites adjacent to any reaction centre,
Cg = concentration of reactant in the gas phase,
Cs = number of reaction sites per sq.cm, of surface,
Cgp = concentration of inhibitor in the gas phase,
f x = partition function of activated complex,
Fg = partition function of reactant for unit volume,
f a = partition function for reactant centres,
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E'0 = heat of activation a t 0° K,

k = Boltzmann’s constant.
Because of the small inhibition by water the A p term may be neglected.
By substituting Fg for a non-linear polyatomic molecule (cf. Glasstone etal. 1941,
p. 374) we obtain

v= 8 v^/
iA
m 8,1,11 e-wT f 1(Sn2)2{S7T3A
)B
m6
(2iT
C

where <r, erl5 are symmetry numbers of reactant and activated complex respectively,
A , B and C are the three moments of inertia of the reactant, m is the mass of a
reactant molecule, and h is Planck’s constant.
Wither = <r1(Glasstone et al. 1941,p. 180);/! = / s (p. 387); S — 4, C8 = 1015(p. 374);
A = 33*2 x 10-40, B = 33*5 x 10-40, C = 2*7 x 10-40 (Lu, Hughes & Giguere 1941);
m = 34/6*06 x 1023; k — 1*37 x 10-16; R —2, h = 6*5
for hydrogen peroxide becomes

Icaic = ~ Ye-°- G2e~E<>i2T

m ol.cm.-2 sec.-1.

If the experimental heat of activation were constant over a wide range of tem ­
perature, this might be substituted for E0. As shown above, however, the apparent
heat of activation decreases with decreasing temperature, the heat of activation of
the surface reaction being considered to be somewhat less than 5500 cal. Assuming
the lower rates to be more representative of the surface reaction we may then
consider the rate at 50° C with activation energy as derived from the data at 15 and
70° C, viz. 4200 cal. The calculated rate a t 1 mm. peroxide pressure is then
0*70 x 1013 mol.cm.-2 sec.-1.
With neglect of the effect of water vapour as before, the experimental rate at
50° C is 0*026[H2O2]2 mm./min. in the reaction vessel of 31*35 ml. volume and
54*0 sq.cm, apparent surface. Expressed in the appropriate units for 1 mm. peroxide
pressure, this becomes 0*76 x 1013 mol.cm.-2sec.-1, in excellent agreement with the
theoretical value.
 220 R. C. Mackenzie and M. Ritchie

Therate of reaction at higher pressures of water

The experimental rates of table 4, showing the effects of alteration of water-
vapour pressure, are in satisfactory agreement with the general rate equation up to
5 mm. water vapour. When, however, the water-vapour pressure was increased
to 10 mm. for the same initial peroxide concentration as before, a pronounced
periodicity appeared in the curve relating the total pressure to the time of decom­
position. For an initial peroxide molar percentage of 75, a t temperature 81-8° C,
pressure readings were recorded every minute; p art of such observations are shown
graphically in figure 2.
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tim e (min.)

F ig u r e 2

Here a periodic decrease in total pressure is to be observed, which is of course

contrary to the normal increase due to the decomposition. The magnitudes of such
decreases and of the increases which follow and precede them are much greater than
any variations arising from irregularities in the thermostat temperatures; at the
pressure involved, the increase in the time period 42-44 min. would correspond to
a temperature change of T5° C, far outside the thermostat variation.
A similar experiment at 120° C showed essentially the same phenomenon. Such
behaviour was also observed at somewhat lower pressures of water vapour although
it became less pronounced as the water vapour pressure decreased; in the range
5-7 mm. water vapour, the magnitudes of the pressure variation wrere of the order
of experimental error. Periodic variations in the rate of decomposition of hydrogen
peroxide have been previously reported for solutions decomposing a t a mercury
surface (Bredig & Weinmayr 1903), but in the vapour phase a mercury surface has
shown no such periodic action (Elder & Rideal 1927).
The present example is of unusual interest in th at an actual decrease in pressure
is recorded, corresponding to an apparent negative rate of reaction. At the relatively
 Thermal decomposition of hydrogen peroxide vapour 221
high pressure of water vapour employed, the amount of water adsorbed on the
vessel walls will be much greater than in the normal decomposition at the low
pressures previously discussed. Since there is no evidence of complex formation
between water and peroxide in the mixed vapours (Elder & Rideal 1927), it is
probable th a t the periodic effect is not due to a gas-phase reaction but is, as before,
dependent on the conditions a t the surface.
The effect of added water is normally to reduce the rate of reaction by factors
representing the decrease in surface available for the adsorption and ultimate
decomposition of the peroxide. I t might be thought possible th at at 10 mm. water-
vapour pressure, the number of available reaction centres would become negligible
and the rate be then not predictable on a statistical basis. The ‘average’ rate,
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however, as given by a smooth curve drawn through the means of pressure is slightly
higher than th a t expected according to the relation holding for lower pressures. This
latter curve is indicated by the discontinuous curve of figure 2. I t would appear,
therefore, th at the main mechanism remains as before but is partly obscured by
some factor related to the high water content. If the added water merely covers
more of the active areas of decomposition, there is no obvious reason why the rate
should depart from the normal in the uncovered areas. The periodic variation must
then be connected with the areas covered by water; on this basis, the total rate
should, in the initial stages at least, be above th at expected by the general formula,
in agreement with the result obtained.
As far as the increases in pressure of figure 2 are concerned, these cannot be
entirely due to peroxide decomposition, because the summation of all these increases
over only the first 60 min. of a run showing an increase of pressure for at least 2 hr.,
is greater than th a t expected from the total amount of peroxide initially present.
They must be accounted for by a non-equilibrium condition involving the expulsion
of water from the surface.
The pressure decreases may arise in two ways. First, adsorption of water and
peroxide may be expected to occur eventually on areas which have been cleared as
above; secondly, peroxide may be removed from the gas phase by solution in the
multimolecular surface layer which water vapour has been considered to form at
higher pressures (Brunauer 1944).
The decomposition of peroxide in aqueous solution is regarded as involving largely
the presence of solid-liquid surfaces, e.g. at dust particles and vessel walls (Rice
1926). In these cases the above solution layers must be concerned. If the reaction is
truly a solid surface phenomenon, then separation of peroxide from the solution
must take place. This, however, is a m atter of some difficulty as shown by the
degree of supercooling which such solutions show. Once such separation has begun,
crystallization becomes rapidly complete; although the two cases are not exactly
parallel, the view may be presented th at the adsorption of peroxide from the water
layer to the solid surface of the vessel is a somewhat similar phenomenon, which,
once begun, rapidly builds up a surface concentration of peroxide considerably
greater than that due to ordinary adsorption of peroxide on a surface free from water.
 222 R. C. Mackenzie and M. Ritchie
The ensuing decomposition of this peroxide aggregate may well be of the nature of
an incipient explosion, with a heat effect resulting in the expulsion of water and
possibly some peroxide from the surface. In normal aqueous solution such heat
effects would be largely dissipated by the large volume of water present, although the
tendency for concentrated peroxide solutions to explode has already been recognized.

Theeffect of oxygen and other gases at higher pressures

In view of the possibility th a t some gas-phase reaction may be present even at
80° C as indicated by the change in tem perature coefficient, and because hydrogen
peroxide is found in small amounts in certain gas reaction systems of much higher
total pressure, some experiments are here quoted in which the pressures of peroxide
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and water remained as before less than 1 mm., while various other gases were added.
The satisfactory application of the general rate equation to previous results had
justified the conclusion th a t the small amounts of oxygen then formed during a
decomposition had no effect on the rate constant, as already indicated also by the
data of table 2 for 8-3 mm. added oxygen. Results obtained a t higher pressures of
oxygen, nitrogen, carbon dioxide and hydrogen are given in table 8.

T able 8

V essel volu m e = 31-35 m l. Tem p. = 82-2° C. [H .O ] = 0-27 m m .

[H 2o 2] [ 0 2] [N 2] [H 2] [C 0 2] 2Ap
mm. mm. mm. mm. mm. m m ./m in.
0-400 — — — — 0-0075
0-400 8-3 — — — 0-0075
0-400 102*2 — — — 0-0040
0-400 169*2 — — — 0-0030
0-400 — 4*3 — — 0-0075
0-400 — 13*5 — — 0-0071
0-400 — 37*8 — — 0-0072
0-400 — 52*9 — — 0-0057
0-400 — 76*3 — — 0-0055
0-400 — 471*6 — — 0-0021
0-600 — — — — 0-0245
0-600 — — 2 — 0-0220
0-600 — — 10 — 0-0205
0-600 — — — 11*4 0-0222

For oxygen and nitrogen there is little appreciable change in the pressure increase
below 10 mm. added gas, but above such pressures a progressive decrease in the
pressure increase is to be observed, which is approximately the same for like pressures
of added gas. I t seems unlikely th a t nitrogen can be involved in any chemical reac­
tion which could produce such effects: more probably some physical phenomenon
is concerned, either alteration of the surface by adsorption or decrease of diffusion
of peroxide to the wall. The adsorptions of nitrogen and oxygen on quartz a t equal
pressures are approximately the same; so also are the diffusion coefficients of a
peroxide molecule diffusing through like pressures of these gases. The results for
 Thermal decomposition of hydrogen peroxide vapour 223
nitrogen can indeed be numerically accounted for by substitution of the factor
(1 + O15[H20 ] 4- 0*002[N2])2 for the denominator of the general rate equation. On
the other hand, calculation shows th a t the diffusion hypothesis is tenable only if the
fraction of peroxide molecule impacts which result in adsorption and decomposition
were of the order 10~7.
The retarding effect of carbon dioxide is not unexpected, by reason of the known
greater adsorption as compared with th a t of oxygen or nitrogen. The decreased rate
of pressure increase in the presence of hydrogen is more probably due to some
chemical reaction in which the pressure does not show the normal increase due to
peroxide decomposition alone.
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Change of reaction vessel

The reaction vessel was replaced by a silica vessel of the same cylindrical shape but
of approximately two-thirds the volume (21*74 ml.). After several attem pts results
became reproducible: an example is given in table 9. Here the initial percentage of
peroxide in the vapour as calculated from the infinity reading is approximately
170 %, whereas experiments with the larger vessel carried out immediately before
the change of vessel gave 98-99 % as expected from the concentration of the reser­
voir peroxide. The results were, however, reproducible and the effect seems genuine.

Table 9
V essel volu m e = 21*74 m l. Tem p. = 83*0° C
t (min.) 0 1 2 5 7 11 21 30 46 52 co
P (mm.) 0*756 0*830 0*895 1*010 1*057 1*121 1*170 1*212 1*243 1*251 1*412

If we consider only the rates during the first 10 min., assuming th a t the initial
pressure of 0*756 mm. represents 98 % peroxide and neglecting the small amount of
water formed during th at time, we find the rates to be no. longer represented by the
bimolecular law but to be more nearly proportional to [H20 2]w, where n = 0*7
(table 10).
Table 10
V essel volum e = 21*74 m l. Tem p. = 83*0° C
t [H 2Oa] -Rexp
m in. mm. m m ./m in. [H 20 2]a/R [H 2Oa]/i? [H 2O 2]07/J?
1 0*607 0*134 2*75 4*5 5*3
3 0*388 0*085 1*77 4*6 6*1
5 0*193 0*060 0*62 3*2 5*3
7 0*138 0*045 0*42 3*1 5*6
9 0*063 0*030 0*13 2*1 4*8

I t is evident from the percentage peroxide as calculated from the ‘infinity’

pressure th at considerable adsorption of peroxide must occur on the surface of this
particular vessel for the given conditions. If the surface were fully saturated an
apparent order of zero would be obtained irrespective of the true order of the reac­
tion; the results above are interpreted as indicating a partial approach to such a state
of affairs.

Vol. 185. A. 15
 224 R. C. Mackenzie and M. Ritchie
It would be expected, however, th a t towards the end of the decomposition such
saturation would no longer be in evidence and th a t the rate should then be of an
apparent order much closer to two. Working from the infinity reading 1-412 mm. the
corresponding H 20 2 and H 20 pressures may be calculated from the recorded pres­
sures over the time interval 15-65 min. (table 11).

T able 11
Vessel volum e = 21-74 m l. Tem p. = 83-0° C

t [H 20 2] [H 20 ] R
m in. m m. mm. m m ./m in. [H 20 2] 2/i?
0-63 0-0140 15
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15 0-46
25 0-36 0-70 0-0065 20
35 0-32 0-73 0-0040 26
45 0-28 0-75 0-0028 28
55 0-24 0-78 0-0020 29
65 0-22 0-79 0-0016 30

W ith neglect again of the possible small effect of the relatively small alteration
in water-vapour pressure, it appears, as shown by the last column, th a t in the later
time stages the reaction is approximately represented by the bimolecular law.
W ith a retarding effect of water of the same magnitude as in the larger vessel, the
velocity coefficient in the bimolecular range is then approximately 1-24/30 = 0-041
in this smaller vessel of apparent surface area 42 sq.cm, as compared with 0-060 for
the larger vessel of 54 sq.cm.; the rates per unit area are satisfactorily concordant
and demonstrate again the surface nature of the reaction.

The authors desire to express their thanks to the Carnegie Trust for a Scholarship
awarded to one of them (R. C. M.), during the tenure of which p art of the above work
was carried out, and to the Moray Fund Trustees for provision of certain apparatus.

R eferences
Bachm an, P . W . & Taylor, G. B. 1929 J. P hys. Chem.
Bredig, G. & W einm ayr, J. 1903 Z. Phys. Chem. 42, 601.
Brunauer 1944 Physical adsorption of gases and vapours. O xford U n iv . Press.
Elder, L. W . & R ideal, E . K . 1927 Trans. Faraday Soc. 23, 545; see also E lder, L. W . 1937
J . Am er. Chem. Soc. 59, 2737.
Giguere, P. A. & Maass, O. 1940 Canad. J . Res. 18 B , 84.
G lasstone, Laidler & E yring 1941 The theory of rate processes. M cGraw-Hill B ook Co.
H inshelw ood, C. N . & Pritchard, C. R . 1923 J . Chem. Soc. 123, 2726.
K ilpatrick, M. L., Reiff, O. M. & R ice, F . O. 1926 J . Am er. Chem. Soc. 48, 3019.
K istiakow sky, G. B . & R osenberg, S. L. 1937 J . Am er. Chem. Soc. 59 , 422.
Lu, C. S., H ughes, E. W. & Giguere, P. A. 1941 J . Am er. Chem. Soc. 63, 1507.
Maass, O. & H atcher, W . H . 1920 J . Am er. Chem. Soc. 42, 2548.
Maass, O. & Herzberg, O. W . 1920 J . Am er. Chem. Soc. 42, 2659.
Maass, O. & H iebert, P. G. 1924 J . Am er. Chem. Soc. 46, 2693.
Rice, F. O. 1926 J . Am er. Chem) Soc. 48, 2099.