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GH. BAKERI
M. RAHIMNEJAD
Faculty of Chemical Engineering,
Babol Noshirvani University of
Technology, Babol, Iran
SCIENTIFIC PAPER
UDC 546.171.5:547.1-3
DOI 10.2298/CICEQ120221061B
CI&CEQ
KINETICS STUDY OF
HYDRAZODICARBONAMIDE
SYNTHESIS REACTION
In this study, the kinetics of hydrazodicarbonamide (HDCA) synthesis reaction
were investigated. Hydrazodicarbonamide is prepared by reaction of urea and
hydrazine in acidic medium. Synthesis of HDCA from urea and hydrazine is a
two-step reaction. In the first step, semicarbazide is synthesized from the reaction of one mole of urea and one mole of hydrazine and in the second step,
semicarbazide reacts with urea to produce hydrazodicarbonamide. By controlling the temperature and pH in the reaction, hydrazine concentration and
the amount of produced hydrazodicarbonamide were measured and using this
data, reaction rate constants were calculated. Based on this study, it was
found that the semicarbazide formation reaction from hydrazine is the ratelimiting step. The rate of semicarbazide synthesis is r1 = 0.1396[NH2NH2]0.5810
and the rate of hydrazodicarbonamide synthesis is r 2 = 0.7715
[NH2NHCONH2]0.8430.
Keywords: hydrazodicarbonamide, azodicarbonamide, semicarbazide,
synthesis, kinetics.
273
NH2
H2N
tration of semicarbazide at the end of synthesis reaction period was calculated by mass balance through
the hydrazine concentration and the weight of precipitated HDCA.
O O
O
H2N NH2 + 2
H2N
HN NH
NH2
H2N
O
H2N
NH2
H2N
NH2
N
H
N
H
NH2
NH3
NH2
H2N
HN NH
NH2 +
274
Figures 1 and 2 represent hydrazine concentration and the weight of precipitated hydrazodicarStep 1
(2)
Step 2
(3)
O O
O
+ H2N
O
+
(1)
+ 2 NH3
NH3
bonamide versus time, while Figure 3 shows the calculated concentration of semicarbazide versus time.
Because the concentration of urea in the
reaction mixture is high, it can be assumed that the
concentration of urea in the reaction mixture is constant and the rate of reactions depend on the concentration of the other components (hydrazine and
semicarbazide). That is, the method of excess is applicable. So the equations for rate of reactions can be
written as follows:
Step 1: -r1 =
dc N
= K1[NH2NH2]n
dt
(3)
Step 2: -r2 =
dc S
= K2[NH2NHCONH2]m
dt
(4)
dc N
= K 1c Nn
dt
cN
c N0
dc N
cN
= K 1dt
0
c N1n c N1n
= K 1t
1 n
0
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0
Time (h)
10
0
0
Time (h)
(c N1n c N10n ) / (1 n ) = K 1t versus time is approximately linear with the slope of K1 [23,24].
The calculation based on optimization methods
of MATLAB software shows that the optimum values
for K1 and n are 0.1396 and 0.5810, respectively. The
value of R2 (coefficient of determination) for optimization is 0.9918. In Figure 4, the concentration of hydrazine versus time is shown for both the experimental
275
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0
Time (h)
Figure 4. Comparison of experimental data and optimization result for hydrazine concentration.
(5)
276
dc S
= K 1c Nn K 2c Sm
dt
(6)
(7)
- 0.7715[NH2NHCONH2]0.8430
urea and hydrazine shows that this reaction is a twostep reaction and each step has its own rate equation.
The plots of hydrazine concentration and semicarbazide concentration versus time show that the
rate of semicarbazide synthesis reaction (reaction of
urea with hydrazine) is lower than the rate of hydrazodicarbonamide synthesis reaction (reaction of
semicarbazide with urea). In the plot of hydrazine
concentration versus time and at t = 1 h, there is a
sudden change in the decreasing trend of hydrazine
concentration versus time which is due to an increase
in semicarbazide concentration in the reaction mixture. This change shows that the first reaction is more
sensitive to semicarbazide concentration. This confirms the conclusion that the rate of semicarbazide
formation reaction is lower than the hydrazodicarbonamide formation reaction and the former reaction is
the rate limiting step for hydrazodicarbonamide synthesis reaction.
The semicarbazide synthesis reaction has the
following rate equation:
-r1 = 0.1396[NH2NH2]0.5810
(8)
CONCLUSIONS
Studying the kinetics of a chemical reaction
allows for more accurate reactor design. The study of
the hydrazodicarbonamide formation reaction from
cN
cS
K1
Figure 5. Comparison of the experimental data and optimization result for semicarbazide concentration.
277
K2
C.H. Lee, S.J. Han, Method for synthesizing hydrazodicarbonamide, US Patent 6635785B1, J&J Chemical Co.
Ltd., 2003
[12]
C.H. Lee, S.J. Han, Method for preparing hydrazodicarbonamide using biuret as starting material, US Patent
7465828, J&J Chemical Co. Ltd., 2008
[13]
Preparation of hydrazodicarbonamide and azodicarbonamide, GB Patent 1146233, Fairmount Chemical Co. Inc.,
1969
[14]
[2]
[15]
[3]
J.P. Schirmann, F. Weiss, Method for manufacturing hydrazodicarbonamide, US Patent 4049712, Produits Chimiques Ugine Kuhlmann, 1977
[16]
[17]
[18]
[19]
C.H. Lee, S.J. Han, Method for preparing hydrazodicarbonamide using biuret as starting material, EP 1513798
B1, J&J Chemical Co. Ltd., 2011
[20]
REFERENCES
[1]
[4]
[5]
[6]
H. Motokawa, T. Hayashi, H. Kohara, Process for the preparation of azodicarbonamides modified with metallic
compounds, US Patent 3876622, Eiwa Chemical Industrial Company, 1975
[21]
[7]
T.H. Newby, J.M. Allen, Preparation of hydrazodicarbonamide, US Patent 2692281, United States Rubber
Company, 1954
[22]
[8]
[23]
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[9]
[10]
278
rd
GH. BAKERI
M. RAHIMNEJAD
Faculty of Chemical Engineering, Babol
Noshirvani University of Technology,
Babol, Iran
NAUNI RAD
279