Acid Catalysis in the Thermal Decomposition of Ammonium Nitrate

Bernard J. Wood and Henry Wise

Citation: The Journal of Chemical Physics 23, 693 (1955); doi: 10.1063/1.1742078
View online: http://dx.doi.org/10.1063/1.1742078
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 23, NUMBER 4 APRIL, 1955

Acid Catalysis in the Thermal Decomposition of Ammonium Nitrate*

BERNARD J. WOOD AND HENRY WISE
Jet Propulsion Laboratory, California Institute of Technology, Pasadena 3, California
(Received July 29, 1954)

Experimental measurements of the kinetics of thermal decomposition of ammonium nitrate have been
made in the temperature range from 443 to 553°K. The results indicate that the degradation of ammonium
nitrate is an autocatalytic liquid-phase reaction, the rate of which is proportional to the product of the mass
of salt and the concentration of acid. The activation energy for this process is found to be 31.4 kcal. Adjust-
ment of the concentration of acid present offers an effective means for the control of the rate of thermal
degradation of ammonium nitrate.

T HE isolation of nitric acid as an intermediate in

the thermal decomposition of ammonium nitrate
was reported by Veley.l Subsequent measurements2 ,3
correlated the amount of acid formed during a given
time interval of reaction to the initial mass of am-
monium nitrate. Nevertheless the mechanism of the
thermal degradation of the salt4 ,5 and in particular the
influence of the acid produced in the reaction are not
known in any detail. In the present analysis a detailed
determination has been carried out of the effect of acid
on the kinetics of thermal decomposition of ammonium
nitrate.
EXPERIMENTAL PROCEDURE
Weighed samples of ammonium nitratet were placed
into carefully dried Pyrex tubes which were subse-
quently evacuated and sealed. The sealed tubes were
immersed for their entire length in an electrically
heated constant-temperature oil bath for various time
intervals. The hot samples were quickly cooled to room
temperature and subsequently frozen in liquid nitrogen
for at least 5 minutes. The frozen ampoules were then
broken, their contents washed into clean beakers with
CO 2-free water, and the resulting solutions titrated
successively for acid with standard potassium hydroxide
and for ammonium ion with formaldehyde solution. 6
In order to provide a definite correlation between
the rate of decomposition of ammonium nitrate and the
amount of nitric acid present, experiments were also
carried out in which known quantities of nitric acid
* This paper presents the results of one phase of research carried
out at the Jet Propulsion Laboratory, California Institute of
Technology, under contract No. DA-04-495-0RD18 sponsored
were added to the salt in the sealed vessel before heating
was commenced. Quantitative transfer of a small but
definite quantity of acid was effected in the following
manner. A glass reservoir of freshly distilled nitric acid
and the ampoule to be charged with acid were con-
nected through separate inlets to a storage bulb of
known volume. The vapor pressure of the acid 7 was
adjusted to the desired value by submerging the acid
reservoir in a thermostated bath. By opening the inter-
vening stopcock, nitric acid vapor was allowed to distill
into the storage bulb until the equilibrium vapor pres-
sure had been established. Then the established concen-
tration of acid isolated in the storage bulb of known
volume was allowed to distill into the evacuated am-
poule which contained NH 4N0 3 , To insure complete
transfer of the vapor from the bulb to the ampoule,
the NH4N0 3 was immersed in liquid nitrogen and
sealed off while still frozen. The quantity of nitric
acid introduced was analyzed volumetrically, and good
agreement was found between the experimental value
and that calculated from the vapor-pressure data for
nitric acid. 7 The reaction products were analyzed by a
procedure identical to that employed in the rate meas-
urements with pure ammonium nitrate,
EXPERIMENTAL RESULTS
The experimental measurements indicate that the
initial rate of decomposition of ammonium nitrate is
proportional to the mass of salt as shown in Fig, 1.
~.2 •
Q
'i 0.2 4
] ..;~ V
~.
."
~e 0.2 0 /'

by the Department of the Army Ordnance Corps. '""'zb'"' V

1 V. H. Veley, J. Chern. Soc. 43, 370 (1883). /'
2 H. L. Saunders, J. Chern. Soc. 121, 698 (1922).
~O.I
• V
...0Z V
3 M. S. Shah and T. M. Oza, J. Chern. Soc. 1932, 725. 0 . 12
4 A. J. B. Robertson, J. Soc. Chern. Ind. 67, 221 (1948). i /]7
6 L. Friedman and J. Bigeleisen, J. Chern. Phys. 18, 1325 (1950).
-~.~ t::::e:
~ 0.08

t The manufacturer's lot analysis ("Baker's Analyzed") lists ;::

the following impurities: ~ 0.0 4 /

Insoluble matter 0.005% heavy metals (as Pb) 0.0002%

0.0001%
§ °lL~~~
:::..-
CI- 0.0002% Fe " 1.00 2.00 300
3
4.00
INITIAL MASS OF NH4 NO, (mol 110 )
P0 4--- 0.0001% N0 2 0.0005%
S04 - - 0.0005% nonvolatile matter 0.0005%
FIG. 1. Initial rate of thermal decomposition as a function of mass
Passes ACS neutrality test. of ammonium nitrate.
6 K. Marcali and W. Rieman, Ind. Eng. Chern., Anal. Ed. 18,
709 (1946). 7 E. P. Egan, Ind. Eng. Chern., Anal. Ed. 37, 303 (1945).
693

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 694 B. J. WOOD AND H. WISE

TABLE II. Effect of nitric acid on decomposition of

~
x o 1/2 gm NH4 NO! AT 4SSoK ammonium nitrate at 448°K.
~6 0 ' - - - • 1/2 om NH 4 NO, AT 503'K IADDEO SURFACE) f-
:~ Initial mass of reactants
• 1/2 gm NH4 N0 3 AT 5030 K Mass of NH,NO.
0"
z mole XIO' decomposed"
NH,NO. HNO. moleXIO'
:r.~
z •0 /
l V V 12.56 0.046 0.21
.....
0"
V 12.50 0.046 0.16
z V
:r.
~ 20 l:I ~
6.21
6.13
6.39
0.046
0.046
0.046
0.14
0.12
0.19
L V
~

,.
iii
0:
L 2.99
3.21
0.046
0.046
0.17
0.13

.V -
li?
o
~ °0
L ~
000 8000 12,000 16,000 20,000
6.25 0.10 0.35

TIME lsec)
" Heating period: 2000 sec; volume of reaction vessel: 4 cc.
FIG. 2. Rate of formation of acid during thermal decomposition
of ammonium nitrate. Consequently the mass rate of decomposition of the
salt is a function only of the mass of acid present in the
However, quantitative analysis of the products further melt. This functional relationship is borne out by the
demonstrates an increasing rate in the production of data in Table II. In these experiments the initial mass
nitric acid during the course of the reaction (Fig. 2). of nitric acid in the sample was kept constant,t how-
It is apparent therefore that the thermal degradation of
ever its concentration was varied by the use of different
ammonium nitrate takes place in the liquid phase and
amounts of ammonium nitrate.
is autocatalyzed by acid.
Based on the rate law [Eq. (1)], the rate constant
In order to determine the effect of acid on the rate
of reaction of ammonium nitrate a number of experi- may be evaluated over the range of temperatures
ments were carried out in the presence of various studied (Fig. 3) and the following rate equation results
amounts of nitric acid which were added to samples of k
salt before heating. The results of these measurements -= e
1014.2 -31400!RT mole- I sec-I. (3)
(Table I) combined with the effect of ullage on the V
amount of ammonium nitrate decomposed (Table III)
indicate that the initial rate of chemical transformation
is proportional to the concentration of acid in the
sample. The experimental results may therefore be
+
N
1\
\
::i
fitted to a rate law of the following form: .,
CJ"

...:
1 da a b ~,oO
---=k-- (1)
...,
T
V dt V V
0
6 ti
where a and b represent the number of moles of am-
I...
0
E \
monium nitrate and acid, respectively, and V, the
volume of the liquid melt. Since V is proportional to
the mass of ammonium nitrate (neglecting the rela-
>
.....
~

I-
Z
\
tively small volume of acid) the rate of disappearance
of the salt (in moles/sec) is also given by
~
(f)
z
0
(.)
W
10
\ 'Y
da k
I-
<t
a::
\
--=-ab=k'b. (2)
dt V
z
0
j:::
'\
~
(.)
<t
TABLE I. Initial rate of decomposition of ammonium nitrate in W
the presence of nitric acid. a::
(.)

~
iL:
Initial mass of reactants Initial decomposi-
U
NH,NO, HNO, w
Temperature tion rate a..
(OK) (mole XIO') (mole X 10') (mole sec-l) XIO' (f) 1.0

448 6.25 1.0 0.008 l"\

448 6.25 11.5 0.075 1.70 1.80 1.90 2.00 2.10 2.20
488 6.25 0.09 0.013 lIT (oK-Ix I03)~
488 6.25 2.0 0.25
488 6.25 11.5 1.2 FIG. 3. Specific reaction rate constant as a function of temperature.
t Except for the last measurement in Table II.

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 THERMAL DECOMPOSITION OF NH 4 N03, CATALYSIS 695

Of special interest is the inhibition in decomposition TABL E III. Effect of ullage on the thermal decomposition of
ammonium nitrate heated 10 000 seconds at 488°K.
rate observed during the course of the reaction (Fig. 4).
This gradual decrease in the rate of decomposition is Initial mass of Mass decomposed (moleX103)
particularly pronounced in those samples of ammonium NH4NO, (mole X103) in reactor of volume
nitrate to which a relatively large amount of nitric
2 cc 4 cc 50 cc
acid originally was added.
Experimental measurements showed conclusively 3.125 0.16 0.16
6.25 0.27 0.28
that the rate of decomposition of ammonium nitrate is 12.50 0.35 0.42 0.50
not affected by such products of reaction as water
vapor§ and nitrous oxide. However the addition of
gaseous ammonia at an initial pressure of 100 mm Hgil dioxide was apparent. ~ These observations are m
almost completely inhibited the reaction at 513°K. agreement with the reported heterogeneous nature of
Additional experiments in which the pressure of am- the thermal decomposition of nitric acid. s
monia was reduced to 10 mm Hgil still showed inhibi-
tion although to a lesser degree. This effect is obviously ANALYSIS OF RESULTS
due to the neutralization of the acid formed as an inter- The course of the thermal decomposition as measured
mediate in the reaction. Since the solubility of am- by the rate of disappearance of ammonium nitrate
exhibits the characteristics of a second-order, auto-
260.----,----,----,,----,----,
• (HNO')ini"al • LOxia" mole
catalytic transformation. It is of interest that the ex-
perimental measurements have demonstrated a linear
• (HNO')inifial ' IL5X 10"mOle
relationship between the rate of decomposition of
ammonium nitrate and the rate of formation of nitric
S! acid, i.e. -c(da/dt) = (db/dt) where c represents an
x2oOr----+--+-+_--~~~_+-----1
(5 I empirical constant whose value O<c<1. Consequently
E I
I at any time t
I
~160r----t~--~~~r---~--__1
Ul
oa. b=c(ao-a)+b o (4)
~
OI20r---_++.__+---~r-~_+--__1 where the subscript zero refers to the initial condition
~ at 1=0. Integration of Eq. (2) yields therefore
o
z
~60r---~----+_--~~--_+----4 V aob
:I:
z kt= In- (5)
(bo+cao) boa
or,
1 b
k't=-ln-.
c bo
2 3 4 5
TIME (sec x 10. 3 ) _
From Eq. (5) the initial mass of acid bo present in the
FIG. 4. Decomposition of ammonium nitrate in the presence of reactant sample may be found by graphical analysis.
nitric acid as a function of time. (c=0.9, Eq. (4) and (6».
Thus a plot of InCb/a) versus time should produce a
straight line whose intercept on the ordinate permits the
monia in liquid ammonium nitrate is smaller than that calculation of boo Such an analysis of the experimental
of the acid, the inhibition does not occur until a suffi- data is presented in Fig. 5.
ciently high concentration of ammonia has accumu-
lated in the vapor phase. This effect is further demon- TABLE IV. Decomposition of ammonium nitrate in the
strated by increasing the volume of the sealed reaction presence of nitric acid at 488°K.
vessel containing the ammonium nitrate (Table III).
Similarly a marked reduction in the rate of decom- Initial mass of reactants
(moleXl()3)
Mass of NH.NO,
Reaction time decomposed
position of ammonium nitrate results from the addi- (sec) NH 4N03 HNO, (moleX103)
tion of surface (glass wool) to the sealed tube containing
the reactants. Thus in the presence of added surface 3000 12.50 0.17
3000 12.50 0.10 0.22&
the concentration of nitric acid and the amount of 3000 12.50 0.10 0.77
ammonium nitrate decomposed was materially reduced
(Table IV). At the same time the formation of nitrogen • With surface added.

§ Friedman and Bigeleisen (see reference 5) reported that small
amounts of water vapor catalyzed the decomposition; however,
such an effect could not be demonstrated in our experimental
measurements.
II Measured at 300 0 K
~ Under these experimental conditions continuous removal of
acid from the liquid phase occurs as long as the rate of thermal
decomposition of acid is fast relative to the rate of vaporization.
S Johnston, Foering, Tao, and Messerly, J. Am. Chern. Soc. 73,
2319 (1951).

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 696 B. J. WOOD AND H. WISE

~ \\,!I)I.\o·!J 488·~
488°K upon the addition of glass wool to the sealed
tube containing the reacting material. As shown by the
~
,-448"

data in Fig. 2, a marked diminution in the final quan-

2t-"
(0,,0,\ I
, \\.SJI. \O-Irl
•.t~
.~
•
.+ tity of HNO a was observed in the presence of added
10' 2 / .
,0 surface. At the same time the formation of nitrogen
.~:~O> dioxide in the gas phase became apparent.
15 \(\",.,O~\
It is also to be remembered that the thermal decom-
· ~ position of ammonium nitrate involves the evolution of

'k'O"O
v." -~O';'I-
ammonia, the solubility of which in liquid ammonium
nitrate is very much smaller than that of nitric acid.

10'
,
O~,
('i'~ V
../ ~ Thus, in a closed reaction vessel as employed in these
experiments, sufficient ammonia may accumulate in the
•
· .~\n~.O:;'-'
/."
~
V
vapor phase to inhibit the reaction. This effect is
readily demonstrated by varying the volume of the
sealed reaction vessel containing the ammonium nitrate
~
~ (Table III).
.~ \(\"'t40~\ A mechanism for the thermal decomposition of am-
monium nitrate which is consistent with the observed
10'
· o ,

TIME (set IC 10',

4 data and with those obtained by other investigations 5 ,9
TABLE V. Initial mass of nitric acid added to NH.N0 3."
FIG. 5. Evaluation of initial mass of acid in liquid melt of ammo-
nium nitrate (initial mass of NH.N03 =6.25XlO-3 mole).
Temperature Mass of acid (mole X 10')
(OK) Added Calculated from Fig. 5
The lower two curves, which represent rate measure-
448 1.0 0.7
ments in the absence of added nitric acid, yield from 448 11.5 11.3
their intercepts on the ordinate O.09XIo- 5 mole of 488 o 0.09
acid at 488°K and O.2XIo-5 mole of acid at 503°K 488 2.0 3.7
488 11.5 13.7
present at the beginning of the chemical transformation. 503 o 0.2
The remaining curves in Fig. 5 represent experimental
measurements in which nitric acid was initially added a Initial mass of ammonium nitrate =6.25 XI0-3 mole; reactor volume
=2 ce.
to the sample. The initial mass of nitric acid evaluated
from these curves is in good agreement with the amount
may be postulated:
of acid actually introduced into the sealed reaction tubes
(see Table V). The presence of acid at the onset of NH 4NO a---c>NH a+HNO a (A)
thermal decomposition of ammonium nitrate is in
accordance with the qualitative observation that acid H++ NH 4NO a---c>[NH 2N0 2]+ HsO+ (B)
can be detected in a sample of the salt heated slightly
[NH 2N0 2]---c>N 20+H 20. (C)
above its melting point, a temperature at which the
rate of decomposition of the material is extremely slow. This sequence of reactions exhibits the catalytic effect
During the initial stages of reaction the experimental of the acidtt and the inhibitory influence of ammonia
results can be fitted to a theoretical curve based on on the decomposition of ammonium nitrate. Equation
Eq. (4) which has the form (B) represents the slow step in the mechanism. Such a
a= (cao+bo)/[c+ (bo/ao)e(ktIV) (ao+cb o)]. (6) dehydration mechanism is based on the findings 5 ,9 that
aN - N bond is formed during the thermal degradation
After prolonged periods of heating, however, the ex- of the salt. On the basis of our work no definite conclu-
perimental data** begin to diverge from the theoretical sion can be drawn concerning the identity of the inter-
curve, especially in the cases in which relatively large mediate. However, isotopic analysis· points to the
amounts of acid were originally added to the sample formation of an unsymmetrical compound such as
(Fig. 4). These deviations are undoubtedly due to the nitramide (NH 2N0 2) which yields the final products by
loss of nitric acid from the liquid phase where it exerts further dehydration.
its autocatalytic action. The accumulation of nitric 9 J. T. Kummer, J. Am. Chern. Soc. 69, 2559 (1947).
acid in the vapor phase was observed indirectly at tt Experimental data by H. A. Bent, [thesis, University of
California (1952)J indicate that sulfuric acid has a similar cata-
** Expressed in the form: (ao- a) vs time. lytic effect.

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