Doklady Physical Chemistry, Vol. 386, Nos. 1–3, 2002, pp. 232–234.

Translated from Doklady Akademii Nauk, Vol. 386, No. 3, 2002, pp. 359–361.
Original Russian Text Copyright © 2002 by Smirnov, Summanen.

PHYSICAL
CHEMISTRY

Rate Oscillations in the Thermal Decomposition

of Aqueous Solutions of Nitric Acid
L. P. Smirnov and E. V. Summanen
Presented by Academician A. G. Merzhanov April 19, 2002

Received May 6, 2002

Nitric acid is finding extensive use in the processes
of production of many substances. In some cases, the
emergency situations arising in these processes are
attributed to the thermal decomposition of nitric acid, in
particular, in aqueous solutions.
This work is a calorimetric experimental study of
the thermal decomposition of aqueous solutions of
nitric acid. Oscillations of the heat absorption rate dur-
ing the decomposition of nitric acid were discovered
for the first time; the influence of the solution concen-
tration and process temperature on self-oscillations was
established.
The decomposition of nitric acid is a reversible
endothermic process with ∆H = 32.5 kJ/mol [1]. The
thermal decomposition of nitric acid and its aqueous
are less regular and have a longer period and larger
amplitude than those for P1 or P2.
The appearance of oscillations may be due both to
the complexity of the reaction mechanism and to the
two-phase character of the reaction system [4], because
evaporation of the acid to the gas phase becomes signif-
icant at temperatures above 410 K [2, 3, 5]. However,
the rate of gas-phase decomposition under our experi-
mental conditions is low [1, 3], and the two-phase char-
acter of the system is unlikely to be the reason for the
oscillations. Apparently, the complex reaction mecha-
nism is responsible for self-oscillations.
The initial composition of the aqueous solution of
nitric acid can be represented as follows [6]:
αHNO 3 + β ( NO 3, H , nH 2 O ) + γHNO 3 ⋅ H 2 O
– +

solutions has been studied repeatedly, but solutions

containing less than 42 wt % of nitric acid have not + γ 3 HNO 3 ⋅ 3H 2 O + δH 2 O,
been studied [1]. The most detailed investigation of this the coefficients being dependent on the solution con-
process has been done by calorimetry [2, 3]. centration (table) and temperature. As the temperature
We studied the thermal decomposition of aqueous increases, α increases, while β and γ3 decrease [7].
solutions of nitric acid on a DAK-1-1 microcalorimeter Water also forms various associates. The mechanism of
in sealed ampoules at temperatures from 417 to 441 K. the liquid-phase decomposition of nitric acid currently
The ratio of the sample mass m to the ampoule volume accepted involves a large number of intermediate prod-
V varied from 0.03 to 0.06 g/cm3. Solutions with con- ucts [1–3, 8], namely,
centrations of 9.9 (P1), 29.7 (P2), and 48.4 (P3) wt % + –
were prepared by diluting reagent grade nitric acid. 2HNO 3 NO 2 + NO 3 + H 2 O, (1)
The resulting kinetic curves are shown in Figs. 1 and +
NO 2 + NO 3
–
N2 O5 , (2)
2. At 417, sample P1 decomposes in a self-oscillating
mode for a long period of time; oscillations are random, N2 O5 NO 2 + NO 3 . (3)
differing both in amplitude and in period and form
(Fig. 1a). The period varies from 5 to 30 min. The The process self-acceleration is due to the reaction
decomposition of samples P2 and P3 proceeds with between HNO3 and NO2:
self-acceleration, no rate oscillations being observed HNO 3 + NO 2 HNO 2 + NO 3 , (4)
for P3; in the case of P2, single oscillations are found at
the initial stage. As temperature increases, oscillations NO 3 NO + O 2 , (5)
become more clearly defined (Fig. 2). At 441 K, the
process follows a self-oscillating pattern over the whole 2NO + O 2 2NO 2 , (6)
range of concentrations studied (Fig. 1b). In the case of
P3, oscillations arise at a later stage of the process; they HNO 2 + HNO 3 2NO 2 + H 2 O. (7)
Institute of Problems of Chemical Physics, It was found [1, 3] that the dependence of the initial
Chernogolovka Branch, Russian Academy of Sciences, rate of HNO3 decomposition on the [HNO3]2/[H2O]
Chernogolovka, Moscow oblast, 142432 Russia concentration ratio has a sharp bend in the region of

0012-5016/02/0009-0232$27.00 © 2002 åÄIä “Nauka /Interperiodica”

 RATE OSCILLATIONS IN THE THERMAL DECOMPOSITION 233

dilute solutions due to the transition from steps (2) and dQ/dt, J/(h g)
(3) to electron transfer between ions (‡)
+ – 0
NO 2 + NO 3 NO 2 + NO 3 . (8)
This fact once again confirms the relationship
between the oscillations and the complex reaction
mechanism because it explains the absence of oscilla- –4
tions in the decomposition of concentrated solutions 2 3
and the presence of oscillations in the case of dilute
solutions of the acid.
–8
The nature of the oscillations can be elucidated
either by mathematical analysis or experimentally. In 1
the former case, one should know the rate constants for
the elementary steps. However, only some of the con- –12
stants appearing in Eqs. (1)–(8) are known. Detailed 10 20 30 40 50 60 70 80
experimental study of the stability of this system (b)
requires a procedure to monitor the concentrations of 32
intermediates during the reaction taking place at ele- 24
vated pressures and temperatures. The development of
such a procedure is a separate complicated problem. 16
The calorimetric technique we used allows one to mea- 1
sure, instead of concentrations, the overall rate of the 8
change in enthalpy caused by the whole set of chemical 0
and physical processes involved. Note that oscillations 2
of the overall rate of heat evolution (or absorption) may –8
differ substantially from the oscillations of concentra-
tions of the intermediate products. –16 3
The contribution of physical processes to the change –24
in enthalpy during the decomposition of nitric acid can
be estimated from the data given in Figs. 1b and 2; they 0 4 8 12 16 20
show that, with an increase in the reaction temperature, t, h
the overall process becomes exothermic at early steps
Fig. 1. Rate of heat evolution (absorption) vs. time dQ/dt
of the decomposition of dilute solutions. This is proba- (per g of the acid) during nitric acid decomposition in an
bly due to the two-phase character of the reaction sys- aqueous solution with a concentration of (1) 9.9, (2) 29.7,
tem. The thermodynamic equilibrium established on and (3) 48.4 wt % at (a) 417 and (b) 441 K.
heating the specimen to the temperature of the experi-
ment is violated, as nitric acid decomposes in the con-
densed phase. As a result, nitric acid molecules pass dQ/dt, J/(h g)
from the gas to the condensed phase, which is accom- 8
panied by heat evolution. The lower the nitric acid con-
centration, the greater the enthalpy change ∆Hevap upon
evaporation from the solution (table). The overall pro-
4
cess remains exothermic until the rate of heat evolution
caused by the transfer of nitric acid to the condensed
phase is higher than the rate of heat absorption due to 2
its decomposition. The competition of these processes, 0
3
one of which is self-accelerated and the other of which
is retarded due to the decrease in the nitric acid content
in the gas phase, accounts for the characteristic pattern –4
of the kinetic curves shown in Figs. 1 and 2. 1
The results of this work allow one to tackle the prob-
lem of oscillations arising in the decomposition of –8
explosives and powders, because water and nitric acid 0 10 20 30 40 50
are among the major products of their decomposition. t, h
The decomposition of explosives and powders usually
Fig. 2. Kinetics of heat evolution (absorption) during
follows a complicated mechanism including reversible, decomposition of nitric acid in an aqueous solution with a
consecutive, and autocatalytic steps [1]. Although such concentration of 29.7 wt % at temperatures of (1) 417,
complex reaction systems may involve the formation of (2) 433, and (3) 441 K.

DOKLADY PHYSICAL CHEMISTRY Vol. 386 Nos. 1–3 2002

234 SMIRNOV, SUMMANEN

Table 1. Composition and properties of aqueous solutions REFERENCES

of nitric acid at 298 K (according to [1, 6])
1. Manelis, G.B., Nazin, G.M., Rubtsov, Yu.I., and Stru-
HNO3 concentration, wt % nin, V.A., Termicheskoe razlozhenie i gorenie
Parameter vzryvchatykh veshchestv i porokhov (Thermal Decompo-
10 30 50 60 sition and Combustion of Explosives and Propellants),
Moscow: Nauka, 1996.
α 0.00 0.00 0.01 0.03
2. Kazakov, A.I., Andrienko, L.P., and Rubtsov, Yu.I.,
β 0.94 0.74 0.39 0.24 Zh. Fiz. Khim., 1979, vol. 53, no. 4, p. 1054.
n 5.8 3.7 2.6 1.6 3. Kazakov, A.I., Andrienko, L.P., and Rubtsov, Yu.I.,
γ1 0.005 0.03 0.19 0.37 Khimicheskaya fizika protsessov goreniya i vzryva
(Chemical Physics of Processes of Combustion and
γ3 0.062 0.23 0.41 0.35 Explosion), Chernogolovka, OIKhF, Akad. Nauk SSSR,
δ 25.8 4.7 1.05 0.48 1977, pp. 71–74.
∆Hevap, kJ/mol 75.5 66.0 44.5 – 4. Ebeling, W., Structurbildung bei irreversilen Prozeccen,
Rostock: BSB B.G. Teubner, 1976.
5. Atroshchenko, V.I. and Kargin, S.I., Tekhnologiya azot-
time- and space-ordered structures [4], no dissipative noi kisloty (Nitric Acid Technology), Moscow: Gosk-
structures have been detected to date in the decomposi- himizdat, 1962.
tion of explosives and powders, because no kinetic data 6. Chedin, M.J., J. Chem. Phys., 1952, vol. 49, no. 1,
on the elementary steps of decomposition obtained pp. 109–125.
with monitoring are available [1]. The results of this 7. Redlich, O., Chem. Rev. 1946, vol. 39, no. 2, pp. 333–
study also demonstrate the necessity of developing 355.
macrokinetic models that take into account the self- 8. Robertson, G.D., Mason, D.M., and Corcolan, W.H.,
oscillation kinetics of the enthalpy change. J. Phys. Chem., 1955, vol. 59, pp. 683–690.

DOKLADY PHYSICAL CHEMISTRY Vol. 386 Nos. 1–3 2002