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Potassium Nitrate Decomposition Paper PURCHASED Fro Acs - Org Michaelstarr1969
Potassium Nitrate Decomposition Paper PURCHASED Fro Acs - Org Michaelstarr1969
FREE~LIN
838
+ CsHs*SH
CcHsSH
+ +CsHaS.*
(14)
Vol. 713
[ C O N T R l B U T I O N F R O M TIIE P Y R O T E C H T I C S CHEMICAL
RESEARCH
LABORATORY,
P I C A T I N S Y .IRSENAL]
The Kinetics of the Thermal Decomposition of Potassium Nitrate and of the Reaction
between Potassium Nitrite and Oxygen1"
BY ELI S. FREE MAN'^
RECEIVED
ACGUST 9, 1956
The kinetics of the thermal decomposition of potassium nitrate were studied in oxygen, at a constant pressure of one
atmosphere, over the temperature range of 650 to 800". The rate of reaction was follomwl by observing changes in volume
as a function of time. From 650 t o 750" the products of decomposition were found t o be potassium nitrite, oxygen and
traces of nitrogen dioxide. Equilibrium was also attained between potassium nitrate, potassium nitrite and oxygen. At
800", decomposition was more extensive, with potassium nitrite decomposing to form nitrogen, oxygen and potassium oxide.
The reaction between potassium nitrite and oxygen was investigated from 550 to 790, by nieasuring the rate of consumptior1
o f oxygen to form potassitmi nitrate. From 550 to 60O0, the reaction gocs slowly to completion. From 650 to 750, equilibriuin was attained between the reactants and potassium nitrate . .4t 790, decomposition of potassium nitrite was evident.
'l%e equilibrium constants of the system were calculated from the data, a n d on the basis of their temperature dependency,
tlie heats of reaction for decomposition and oxidation were determined. :I reaction tnecllanism is proposed and the kinetics
of the reactions as well as the energies of activation were ev:iluated. In addition, sonic of the results of this study are conipared with those obtained in a previous investigation of sodium nitrate and sodiurn nitrite.
(1) (a) This paper was presented, in part, before t h e Division of
Physical and Inorganic Chemistry a t t h e North Jersey M e e t i n g in
hliniature of t h e American Chemical Society in Xervark, N. J , , Janu-
ary 1956, and a t t h e Delauare Valley Regional hieeting in Philadelphia, P a . , February 1956; (b) T h e Newark Colleges of Rutgers University, Xervark 2 , h-.J.
THERMAL
DECOMPOSITION
O F POTASSIUM NITRATE
: KINETICS
s39
Introduction
Due to the extensive use of alkali nitrates in
pyrotechnics, explosives, rocket ignitors as well as
in metallurgical heat treating, there is considerable
interest in the high temperature behavior of these
salts. Previous work dealt, primarily, with the
identification of the reaction products and the determination of the decomposition temperature^.^-^
Much of the former work, however, was carried
out in quartz which led to confusing results due
to a reaction between silica and the nitrates.
This investigation is concerned with the reaction kinetics of the thermal decomposition of potassium nitrate. The reaction between potassium
nitrate and oxygen was also studied to aid in the
elucidation of the mechanism of decomposition.
Some of the results of this investigation are compared with the results obtained from a similar
study of sodium nitrate and sodium nitrite.6
Experimental
T h e potassium nitrate and potassium nitrite were purchased from the Fisher Scientific Co. and were of C.P.
Grade. The oxygen, 99.8y0 pure, was obtained from the
Matheson Co. Of several types of reaction vessels tested,
it was found that stainless steel 317 was suitable for this
study. Spectroscopic analyses of melts which were heated
to the experimental temperatures showed that the extent
of attack on the stainless steel vessels was negligible over
the experimental times. Furthermore, the inner surface
did not appear to catalyze the reaction since varying the dimensions of the vessel had no significant effect on the rate
of decomposition.
T h e experimental procedure and apparatus are identical
to that used previously6; the gases, however, were analyzed
by the Orsat m e t h ~ d . T
~ h e reactions were carried out in
oxygen, a t one atmosphere of pressure, in Type 317 stainless steel tubes. The dimensions of these vessels are 0.1
cm. wall thickness, inside diameter, 1.6 cm. and 1.3 cm.,
length, 13 cm. Unless otherwise mentioned, the reactions
were conducted in the tubes having a n inside diameter of
1.6 cm. X-Ray analysis was used t o identify the solid
products.
30 40 50 60 70 80 90
Time, min.
Fig. 1.-The decomposition of potassium nitrate in oxygen
(1 atm.), temp., OC.: 0, 650; A, 700; 0, 750; 0 , 800.
10
20
K , = equilibrium constant
Nl and N2 = mole fraction of potassium nitrate or nitrite,
depending on whether decomposition or
oxidation is cotlsidered
ELI s. FREERIAN
s40
Vol. 79
Correspondiiig temp., C .
747
707
671
637
10
20
:3 0
40
.8l F
.G
y;;;
0.9so
1.020
1.060
1.100
x 103, O K . - ~ .
Fig. 3.-Temperature
dependency of equilibrium coilstants: A , right coordinate, KN03 = KXOz
* / 2 0 2 ; 0,
left coordinate, l / * 0 2
K N 0 2 = KNOa.
T-1
30
100
110
120
50
150
200 250 300
Time, min.
Fig. 2.-The
reaction between potassium nitrite and
oxygen (1 a t m . ) , temp., C . : (23, 550; 69,600; 0,650;
A , 700; 0,750; 0,790.
100
are approximately the same. Furthermore, systems generally approach ideality a t high temperatures. The activity coefficients were therefore taken as unity. The respective mole fractions
of potassium nitrate and nitrite were determined
from the amount of oxygen evolved or consumed
during reaction up t o the time of equilibrium.
The equilibrium constants, determined from the
reaction between potassium nitrite and oxygen are
reasonably close to the reciprocals of the equilibrium constants as obtained from the decomposition studies. These values are 14.0, 4.6, 1.9 and
14.1, 5.2 and 2.4 a t 750, 700 and 650, respectively.
It should be noted that a small error in the measured volume results in a relatively large error in
the calculated equilibrium constants. For example, a t 650 a difference of 5yo in the volume at
equilibrium resulted in a l2Yb variation between
the cqiiilibriuni constants.
Figure 3, log Ke us. T- shows the temperature
dependency of the equilibrium constants. The
heats of reactions evaluated from the slopes of the
lines are 30.8 and -32.8 kcal. mole- for the decomposition of potassium nitrate and the reaction
between potassium nitrite and oxygen, respectively.
+ kl_ KNO3 f 0
KXOs + O k r _ K S O a
KNOs kr_ KXOa + 0
KNOa + 0 K,_ &SO? + 0:
KSOY
0 2
(2)
(3)
(4)
(3)
THERMAL
DECOMPOSITION
OF POTASSIUM
NITRATE: KINETICS
dt
kl,k2,ka1k4 =
- k&KNOsNO
(6)
rate constants
561
+ kzNKNo2Nok3NKN03
N = mole fraction
841
40
60
0.900
1.000
T-*
1.100
103, O K . - ~ .
1.200
12
10
c
dNKNOs
--
- kl'NKNo2
dt
X
- 8
5,
k i t , kz',
At equilibrium dNKN03/dt = 0.
equation is therefore obtained
j
:
6 6
xe
x
a
t
\
-0
A
5 4
hl
The following
-X)
= time
(8)
+ k,
= initial no. of moles of potassium nitrate
Kz =
(9)
k3
10
15
20
Time, min.
Fig. 5.-Kinetics of the decomposition of potassium nitrate
in oxygen (1 atm.), temp., O C . : 0, 600; A , 700; E , 750.
5