Mechanisms and Kinetics of the Synthesis of FOX-12†

doi:10.7503/cjcu20140873

Abstract

Abstract:

The mechanisms of the synthesis of N-guanylurea-dinitramide(FOX-12) were investigated at B3LYP/6-311G(d,p) level. The geometries of the reactants, intermediates, transition states, and products were optimized, respectively. The relevance between every transition state and the corresponding reactant/product was confirmed via the intrinsic reaction coordinates(IRC). The single-point energies of the species at the optimized geometries were corrected at the MP2/6-311++G(3df,3pd) level. It was shown that the binitro-amide acid(HDN) could be obtained by both channel A1, in which —SO₃ was preferentially replaced by nitronium(N $O 2 +$ ), and channel B, in which —H was preferentially replaced by N $O 2 +$ , while the channel A1 was found to be the dominant channel. Then the intermediate product of HDN could be converted to the targeted product of FOX-12 via the channel of either HDN→FOX-12 or HDN→amonium dinitramide(ADN)→FOX-12, while the latter was tend to be considered as the better approach. The rate constants were calculated at temperature ranges of 200—400 K by means of the classical transition state theory(TST) and the canonical vibration transition state theory(CVT) corrected by the small-curvature tunneling(SCT). And the three-parameter Arrhenius expressions of rate constants were also provided. It was expected that the present study may provide a theoretical basis to the research and engineering amplification of FOX-12 as well as other energetic materials.

Key words: N-Guanylurea-dinitramide(FOX-12), Mechanism, Rate constant, Quantum chemistry calculation

CLC Number:

O643.1

TrendMD:

WANG Kuan, CHEN Jiangang, WANG Bozhou, LU Jian, WANG Wenliang, LIU Fengyi, ZHOU Cheng, LIAN Peng, LIU Zhongwen, LIU Zhaotie. Mechanisms and Kinetics of the Synthesis of FOX-12^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 531.

Figures/Tables 8

Table 1 Zero-point energies(ZPE), relative energies[ΔE and(ΔE+ZPE)], enthalpies(ΔH), and free energies(ΔG) of reactants, products, transition states, and intermediates during the synthesis process of FOX-12

Route	Species		ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		(ΔE+ZPE)/(kJ·mol^-1)
Route	Species		ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		B3LYP	MP2
A	NH₂S $O 3 -$ +2N $O 2 +$ +HS $O 4 -$		234.11		0		0		0	0
	A-IM1+N $O 2 +$ +HS $O 4 -$		236.58		-617.13		-659.09		-658.12	-579.15
	A-TS1+N $O 2 +$ +HS $O 4 -$		235.83		-527.28		-574.70		-571.52	-517.61
	A-IM2+N $O 2 +$ +HS $O 4 -$		238.95		-662.48		-693.19		-693.50	-615.60
	A1-IM3+SO₃		242.54		-1231.37		-1307.64		-1306.55	-1161.46
	A1-TS2+SO₃		234.08		-1163.15		-1249.01		-1245.34	-1126.87
	A1-IM4+SO₃		242.56		-1270.19		-1352.04		-1349.98	-1220.69
	A2-IM3+SO₃+HS $O 4 -$		234.47		-695.28		-720.00		-719.45	-608.41
	A2-TS2+SO₃+HS $O 4 -$		222.85		-548.53		-578.98		-576.74	-459.56
	A2-IM4+SO₃+HS $O 4 -$		235.61		-667.95		-701.59		-698.96	-555.50
B	B-IM1+N $O 2 +$		239.72		-691.83		-783.65		-781.62	-694.39
	B-TS1+N $O 2 +$		239.06		-595.52		-691.98		-688.35	-629.50
	B-IM2+N $O 2 +$		247.11		-794.49		-886.47		-883.68	-812.49
	B-IM3+H₂SO₄		243.02		-1221.70		-1309.81		-1306.36	-1174.61
	B-TS2+H₂SO₄		239.73		-1146.81		-1238.48		-1234.21	-1132.00
	B-IM4+H₂SO₄		240.14		-1250.95		-1323.35		-1322.95	-1192.61
	HDN+SO₃+H₂SO₄		237.91		-1279.82		-1315.89		-1312.71	-1167.02
HDN→FOX-12	R+HDN		379.06		0		0		0	0
Route	Species	ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		(ΔE+ZPE)/(kJ·mol^-1)
Route	Species	ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		B3LYP		MP2
HDN→FOX-12	IM1	378.82		-30.79		-74.93		-76.38		-75.23
	TS1	372.62		-34.22		-82.20		-82.08		-79.37
	IM2(FOX-12)	379.85		-58.76		-103.05		-104.68		-96.80

Route	Species		ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		(ΔE+ZPE)/(kJ·mol^-1)
Route	Species		ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		B3LYP	MP2
A	NH₂S $O 3 -$ +2N $O 2 +$ +HS $O 4 -$		234.11		0		0		0	0
	A-IM1+N $O 2 +$ +HS $O 4 -$		236.58		-617.13		-659.09		-658.12	-579.15
	A-TS1+N $O 2 +$ +HS $O 4 -$		235.83		-527.28		-574.70		-571.52	-517.61
	A-IM2+N $O 2 +$ +HS $O 4 -$		238.95		-662.48		-693.19		-693.50	-615.60
	A1-IM3+SO₃		242.54		-1231.37		-1307.64		-1306.55	-1161.46
	A1-TS2+SO₃		234.08		-1163.15		-1249.01		-1245.34	-1126.87
	A1-IM4+SO₃		242.56		-1270.19		-1352.04		-1349.98	-1220.69
	A2-IM3+SO₃+HS $O 4 -$		234.47		-695.28		-720.00		-719.45	-608.41
	A2-TS2+SO₃+HS $O 4 -$		222.85		-548.53		-578.98		-576.74	-459.56
	A2-IM4+SO₃+HS $O 4 -$		235.61		-667.95		-701.59		-698.96	-555.50
B	B-IM1+N $O 2 +$		239.72		-691.83		-783.65		-781.62	-694.39
	B-TS1+N $O 2 +$		239.06		-595.52		-691.98		-688.35	-629.50
	B-IM2+N $O 2 +$		247.11		-794.49		-886.47		-883.68	-812.49
	B-IM3+H₂SO₄		243.02		-1221.70		-1309.81		-1306.36	-1174.61
	B-TS2+H₂SO₄		239.73		-1146.81		-1238.48		-1234.21	-1132.00
	B-IM4+H₂SO₄		240.14		-1250.95		-1323.35		-1322.95	-1192.61
	HDN+SO₃+H₂SO₄		237.91		-1279.82		-1315.89		-1312.71	-1167.02
HDN→FOX-12	R+HDN		379.06		0		0		0	0
Route	Species	ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		(ΔE+ZPE)/(kJ·mol^-1)
Route	Species	ZPE/ (kJ·mol^-1)		ΔG(298 K)/ (kJ·mol^-1)		ΔH(298 K)/ (kJ·mol^-1)		B3LYP		MP2
HDN→FOX-12	IM1	378.82		-30.79		-74.93		-76.38		-75.23
	TS1	372.62		-34.22		-82.20		-82.08		-79.37
	IM2(FOX-12)	379.85		-58.76		-103.05		-104.68		-96.80

Fig.1 Optimized geometries of species of the channels in replacing-SO3 first calculated at B3LYP/6-311G(d,p) level of theory Bond length units are in nm.

Fig.2 Energy diagram for the potential energy surface of each nitration path of NH2SO3- in mixed nitric-sulfuric acid predicted at the MP2/6-311++G(3df,3pd)//B3LYP/6-311G(d,p) level of theory

Fig.3 Optimized geometries of species of priority to replacing H channels calculated at B3LYP/6-311G(d,p) level of theory Bond length units are in nm.

Fig.4 Proposed synthesis pathways for FOX-12

Fig.5 Schematic energy diagram for the potential energy surface of the formation of FOX-12, which directly synthesized from HDN, obtained at the MP2/6-311++G(3df,3pd)//B3LYP/6-311G(d,p) level of theory Bond length units are in nm.

Table 2 Calculated rate constants(cm3·molecule-1·s-1) of the elementary reactions during the nitration of NH2SO3- in mixed nitric-sulfuric acid at temperature ranges of 200—400 K

T/K	$k TA - 1 CVT / SC$	$k A 1 - 2 CVT / SCT$	$k A 2 - 2 CVT / SCT$	$k B - 1 CVT / SCT$	$k B - 2 CVT / SCT$
200	6.56×10^-5	4.64×10^-3	1.01×10^-10	1.09×10^-5	5.98×10¹¹
220	1.13×10^-3	5.08×10^-2	9.87×10^-10	7.39×10^-4	5.23×10¹¹
233	5.38×10^-3	1.92×10^-1	3.67×10^-9	2.87×10^-3	4.82×10¹¹
255	5.43×10^-2	1.32×10⁰	2.65×10^-8	2.21×10^-2	4.25×10¹¹
265	1.39×10^-1	2.85×10⁰	6.00×10^-8	5.11×10^-2	4.03×10¹¹
270	2.17×10^-1	4.09×10⁰	8.87×10^-8	7.61×10^-2	3.94×10¹¹
273	2.81×10^-1	5.05×10⁰	1.12×10^-7	9.62×10^-2	3.88×10¹¹
276	3.63×10^-1	6.20×10⁰	1.40×10^-7	1.21×10^-1	3.83×10¹¹
280	5.07×10^-1	8.10×10⁰	1.88×10^-7	1.64×10^-1	3.76×10¹¹
285	7.60×10^-1	1.12×10¹	2.71×10^-7	2.36×10^-1	3.68×10¹¹
295	1.65×10⁰	2.06×10¹	5.45×10^-7	4.75×10^-1	3.54×10¹¹
300	2.38×10⁰	2.76×10¹	7.64×10^-7	6.64×10^-1	3.47×10¹¹
305	3.41×10⁰	3.65×10¹	1.07×10^-6	9.21×10^-1	3.41×10¹¹
310	4.83×10⁰	4.79×10¹	1.47×10^-6	1.27×10⁰	3.36×10¹¹
315	6.78×10⁰	6.22×10¹	2.03×10^-6	1.73×10⁰	3.30×10¹¹
320	9.42×10⁰	8.02×10¹	2.78×10^-6	2.33×10⁰	3.25×10¹¹
325	1.30×10¹	1.02×10²	3.78×10^-6	3.13×10⁰	3.21×10¹¹
330	1.77×10¹	1.30×10²	5.11×10^-6	4.17×10⁰	3.17×10¹¹
335	2.40×10¹	1.63×10²	6.89×10^-6	5.52×10⁰	3.13×10¹¹
340	3.22×10¹	2.04×10²	9.25×10^-6	7.25×10⁰	3.09×10¹¹
350	5.68×10¹	3.13×10²	1.65×10^-5	1.23×10¹	3.03×10¹¹
360	9.74×10¹	4.67×10²	2.88×10^-5	2.03×10¹	2.97×10¹¹
370	1.63×10²	6.81×10²	4.99×10^-5	3.28×10¹	2.93×10¹¹
380	2.65×10²	9.74×10²	8.52×10^-5	5.19×10¹	2.89×10¹¹
400	6.58×10²	1.88×10³	2.41×10^-4	1.23×10¹	2.84×10¹¹

Table 2 Calculated rate constants(cm3·molecule-1·s-1) of the elementary reactions during the nitration of NH2SO3- in mixed nitric-sulfuric acid at temperature ranges of 200—400 K

T/K	$k TA - 1 CVT / SC$	$k A 1 - 2 CVT / SCT$	$k A 2 - 2 CVT / SCT$	$k B - 1 CVT / SCT$	$k B - 2 CVT / SCT$
200	6.56×10^-5	4.64×10^-3	1.01×10^-10	1.09×10^-5	5.98×10¹¹
220	1.13×10^-3	5.08×10^-2	9.87×10^-10	7.39×10^-4	5.23×10¹¹
233	5.38×10^-3	1.92×10^-1	3.67×10^-9	2.87×10^-3	4.82×10¹¹
255	5.43×10^-2	1.32×10⁰	2.65×10^-8	2.21×10^-2	4.25×10¹¹
265	1.39×10^-1	2.85×10⁰	6.00×10^-8	5.11×10^-2	4.03×10¹¹
270	2.17×10^-1	4.09×10⁰	8.87×10^-8	7.61×10^-2	3.94×10¹¹
273	2.81×10^-1	5.05×10⁰	1.12×10^-7	9.62×10^-2	3.88×10¹¹
276	3.63×10^-1	6.20×10⁰	1.40×10^-7	1.21×10^-1	3.83×10¹¹
280	5.07×10^-1	8.10×10⁰	1.88×10^-7	1.64×10^-1	3.76×10¹¹
285	7.60×10^-1	1.12×10¹	2.71×10^-7	2.36×10^-1	3.68×10¹¹
295	1.65×10⁰	2.06×10¹	5.45×10^-7	4.75×10^-1	3.54×10¹¹
300	2.38×10⁰	2.76×10¹	7.64×10^-7	6.64×10^-1	3.47×10¹¹
305	3.41×10⁰	3.65×10¹	1.07×10^-6	9.21×10^-1	3.41×10¹¹
310	4.83×10⁰	4.79×10¹	1.47×10^-6	1.27×10⁰	3.36×10¹¹
315	6.78×10⁰	6.22×10¹	2.03×10^-6	1.73×10⁰	3.30×10¹¹
320	9.42×10⁰	8.02×10¹	2.78×10^-6	2.33×10⁰	3.25×10¹¹
325	1.30×10¹	1.02×10²	3.78×10^-6	3.13×10⁰	3.21×10¹¹
330	1.77×10¹	1.30×10²	5.11×10^-6	4.17×10⁰	3.17×10¹¹
335	2.40×10¹	1.63×10²	6.89×10^-6	5.52×10⁰	3.13×10¹¹
340	3.22×10¹	2.04×10²	9.25×10^-6	7.25×10⁰	3.09×10¹¹
350	5.68×10¹	3.13×10²	1.65×10^-5	1.23×10¹	3.03×10¹¹
360	9.74×10¹	4.67×10²	2.88×10^-5	2.03×10¹	2.97×10¹¹
370	1.63×10²	6.81×10²	4.99×10^-5	3.28×10¹	2.93×10¹¹
380	2.65×10²	9.74×10²	8.52×10^-5	5.19×10¹	2.89×10¹¹
400	6.58×10²	1.88×10³	2.41×10^-4	1.23×10¹	2.84×10¹¹

Fig.6 Logarithms of the calculated rate constants in the rate-limiting step of path A1 at temperature ranges of 200—400 K

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