Quantum chemistry calculation for isopropyl nitrate hydrolysis reaction

Abstract

Two kinds of isopropyl nitrate hydrolysis reaction mechanism are calculated theoretically. The geometry frequencies of reactants and products are calculated with MP2 method. The solvation effect is investigated at the same level. The results show that the reaction tends to be nucleophilic substitution reaction when temperature is high. And the reaction potential energy in solution state is much lower than that in standard state. The calculation results can be useful for further research.

Keywords

Hydrolysis reaction isopropyl nitrate quantum chemistry MP2 method

1. Introduction

Isopropyl nitrate is a kind of nitrate esters which plays an important role in national defense industry. Isopropyl nitrate can not only be used as warhead charge, but also as rocket propellant. It is a highly volatile and toxic material with strong oxidizing. The waste isopropyl nitrate should be treated properly. However, there is still no safe and environmental treatment for isopropyl nitrate at present. Isopropyl nitrate hydrolysis reaction is a suitable method to treat waste isopropyl nitrate.

Figure 1 shows the geometry of isopropyl nitrate. According to Fig. 1, isopropyl nitrate has a nitroxyl(-C-O-NO ${}_{2}$ ). The nitro group is linked to carbon atom by an oxygen atom, which is the characteristic of nitrates. It means that isopropyl nitrate is a kind of O-nitrocompound.

The hydrolysis reaction is an effective and easy method to treat nitrates. The hydrolysis reaction mechanism of nitrates is similar to the hydrolysis reaction mechanism of carboxylic esters. The bond fracture in carboxylic esters hydrolysis reaction with acid or alkali can be divided into two types: acyloxy bond fracture and alkoxy bond fracture. This can be confirmed from the corresponding esterification reaction mechanism of carboxylic acids and alcohols. There are two kinds of bond fracture modes in the esterification reaction of simple carboxylic acid and alcohol. The first one is that the hydroxyl -OH in carboxylic acid and the hydrogen in alcohol are combined into water molecule. The rest forms the ester. Since the carboxylic acid becomes an acyl group after the hydroxyl -OH is off, this bond fracture mode is known as the acyloxy bond fracture. The second mode is the hydrogen of the carboxylic acid and the -OH in the alcohol combining into water, which is called the alkoxy bond fracture.

Figure 1.

The geometry of isopropyl nitrate.

The acid hydrolysis is a reversible reaction, and the alkaline hydrolysis reaction is irreversible. The alkaline hydrolysis reaction is more thoroughly. Therefore the alkaline hydrolysis reaction method is used for the treatment of isopropyl nitrate. The hydrolysis of alkyl nitrates under alkaline condition has three competitive reaction mechanism, including nucleophilic substitution reaction (S ${}_{\rm N}$ 2), $\alpha$ -H elimination reaction (E ${}_{\alpha}$ ) and $\beta$ -H elimination reaction (E ${}_{\beta}$ ).

$\displaystyle\rm RCH_{2}CH_{2}ONO_{2}+OH^{-}\to RCH_{2}CH_{2}OH+ONO_{2}^{-}$ $\displaystyle\rm RCH_{2}CH_{2}ONO_{2}+OH^{-}\to RCH_{2}CH_{2}O+H_{2}O+NO_{2}^{-}$ $\displaystyle\rm RCH_{2}CH_{2}ONO_{2}+OH^{-}\to RCH=CH_{2}+H_{2}O+ONO_{2}^{-}$

The direction and rate of hydrolysis reaction are mainly determined by molecular structure and environmental effects. The kinetic experiments showed that the alkaline hydrolysis reaction of alkyl nitrate is S ${}_{\rm N}$ 2 reaction.

The hydrolysis reaction is an effective and easy method to treat isopropyl nitrate. There are some related theoretical researches about the isopropyl nitrate property and alkaline hydrolysis reaction [1, 2, 3, 4, 5, 6, 7, 8]. It is generally believed that alkaline hydrolysis reaction of isopropyl nitrate can generate nitrate and isopropanol.

True [9] explored the configuration of isopropyl nitrate through experiments. Thornton [11] made theoretical inference about the hydrolysis mechanism according to classical mechanics. Zeng et al. [10] used B3LYP, B3PW91 and B3P86 method with 6-31 $+$ G* and 6-311 $+$ G* basis set to optimize geometric structure of isopropyl nitrate and calculate the energy of the lowest unoccupied molecular orbital(LUMO) and the energy of the highest occupied molecular orbital(HOMO). The bond dissociation energies(BDE) of O-NO ${}_{2}$ were obtained. It is found that the thermal decomposition of isopropyl nitrate is the hemolytic reaction of O-NO ${}_{2}$ based on the activation energy calculation. Gong et al. [12] used SCF-MOAM1 method to calculate the geometric structure of isopropyl nitrate in standard state. The activation energy of S ${}_{\rm N}$ 2 reaction calculated by Gong with AM1 method was 18.10 Kcal/mol in standard state. The geometric structure and charge distribution of the system during the hydrolysis reaction process were also discussed. Liu et al. [13] calculated the geometric structure of isopropyl nitrate at B3LYP/6-31 $++$ G(d,p) level. The thermal decomposition reaction of isopropyl nitrate was calculated with AM1 method. The S ${}_{\rm N}$ 2 reaction of isopropyl nitrate hydrolysis reaction was calculated with DFT method in standard state. It is found that the alkaline hydrolysis activation energy was 12.55 Kcal/mol, which was calculated at B3LYP/6-31 $+$ G(d) level. Wang and Xiao [14] used MINDO/3 method to obtain the geometric geometry and potential curves of the S ${}_{\rm N}$ 2 reaction for five kinds of alkyl nitrates. The alkaline hydrolysis activation energy was calculated. The substituent effect was also discussed. According to the calculation results, the hydrolysis activation energies of these alkyl nitrates which have short carbon chain are low, especially CH ${}_{3}$ NO ${}_{2}$ . CH ${}_{3}$ NO ${}_{2}$ only has two groups. The small space barrier leads to the low activation energy. The space barrier becomes larger when the hydrogen connected with $\alpha$ -C atom of alkyl nitrate is substituted by methyl group. The energy of the lowest unoccupied molecular orbital (LUMO) becomes higher and the hydrolysis activation energy is higher.

In this paper, two routes of isopropyl nitrate alkaline hydrolysis reaction are considered. Reaction 1 (R1) is nucleophilic substitution (S ${}_{\rm N}$ 2) reaction. The products of R1 are isopropanol and nitrate ion. Reaction 2 (R2) is $\beta$ -hydride elimination (E ${}_{\beta}$ ) reaction. The products of R2 are propylene, nitrate ion and water.

2. Calculation methods

All electronic structure and energy calculations are carried out with Gaussain 09 program package. The optimized geometries and harmonic vibrational frequencies of all stationary points are obtained at second order Møller-Pleset perturbation theory(MP2) [15, 16, 17, 18] with the 6-311 $+$ g(d,p) basis set. Carry out closed-shell calculation for the system. At the same level, the minimum-energy path (MEP) was obtained by intrinsic reaction coordinate (IRC) theory to confirm that the transition states connect with the right reactants and products.

In order to discuss the solvation effect on the alkaline hydrolysis reaction of isopropyl nitrate, the thermodynamic parameters and potential energy curves of the four alkaline hydrolysis reaction pathways are obtained at MP2/6-311 $+$ g(d,p) level in standard state and solution state with Polarizable Continuum Model (PCM) [19, 20, 21, 22].

3. Results and discussion

3.1 Reaction mechanism

According to the geometry of isopropyl nitrate and reaction mechanism in Fig. 2, there is only one pathway for hydroxyl attacking the middle carbon atoms, which is the S ${}_{\rm N}$ 2 reaction. And there are three pathways for hydroxyl attacking the hydrogen atoms of the terminal methyl group, which is the E ${}_{\beta}$ reaction. Therefore, the process of isopropyl nitrate alkaline hydrolysis reaction including four reaction pathways in all is investigated.

Pathway 1: Pathway 1:
Hydroxyl attacks the middle carbon atoms of isopropyl nitrate from the back. The reaction products are isopropanol and nitrate ions.
Pathway 2:
Hydroxyl attacks hydrogen atom 9 connected with the terminal carbon of isopropyl nitrate. The reaction products are propylene, water and nitrate ions.
Pathway 3:
Hydroxyl attacks hydrogen atom 10 connected with the terminal carbon of isopropyl nitrate. The reaction products are propylene, water and nitrate ions.
Pathway 4:
Hydroxyl attacks hydrogen atom 8 connected with the terminal carbon of isopropyl nitrate. The reaction products are propylene, water and nitrate ions.

Figure 2.
Geometries of all reactants and products.

In R1, the hydroxyl attacks the middle carbon atom C ${}_{5}$ from backside and forms complex 1 firstly. The O atom of the hydroxyl gradually gets closer to C ${}_{5}$ . The C5-O ${}_{11}$ bond elongates and transition state (TS) is formed. And then the hydroxyl loses an electron and combines with C ${}_{5}$ . C ${}_{5}$ -O ${}_{11}$ bond breaks, O ${}_{11}$ gets an electron, and complex 2 is formed. Finally, the decomposition of complex 2 produces nitrate ion and isopropanol. In R2, the hydroxyl ion attacks the hydrogen atom connected with the terminal carbon of isopropyl nitrate and forms complex 1 firstly. The O atom of the hydroxyl gradually gets closer to the hydrogen atom connected with the terminal carbon in the rear of the carbon chain. The C ${}_{5}$ -O ${}_{11}$ bond elongates and transition state is formed. And then the C-H bond of the terminal carbon breaks, the hydrogen atom combines with the hydroxyl. The terminal carbon atom combines with C ${}_{5}$ and forms carbon-carbon double bond. C ${}_{5}$ -O ${}_{11}$ bond breaks, O ${}_{11}$ gets an electron, and complex 2 is formed. Finally the decomposition of complex 2 produces propylene, water and nitrate.

In this way, four transition states of each reaction pathway are located. The geometries of all reactants, transition states and products in four reaction paths are optimized at MP2/6-311 $+$ g(d,p) level.

Figure 2 shows the geometric parameters including bond distances and angles of all reactants and products.

The harmonic vibrational frequencies of reactants, products and four transition states of four pathways are calculated at MP2/6-311 $+$ g(d,p) level. Calculation results are in Table 1. From Table 1, it can be known that the vibrational frequencies of reactants and products are positive, and the frequencies of each transition state only have one imaginary frequency. The stretching vibration frequency of the O-H bond of isopropanol is 3819 cm ${}^{-1}$ , vibration frequency of hydroxyl ion is 3309 cm ${}^{-1}$ , the anti-symmetry and symmetry stretching vibration frequencies of N-O bond are 1045 and 1370 cm ${}^{-1}$ . These experimental results are basically consistent with the calculation results.

Table 1
Vibrational frequencies of reactants, transition states and products. Among them, TS1, TS2, TS3 and TS4 are respectively the transition states of pathway 1, 2, 3, 4

Frequencies (cm ${}^{-1}$ )

Isopropyl nitrate 77, 107, 209, 221, 273, 330, 416, 461, 578, 729, 760, 860, 895, 950, 966, 980, 1155, 1195, 1221, 1303, 1371, 1404, 1425, 1435, 1497, 1502, 1516, 1529, 1841, 3080, 3083, 3129, 3169, 3177, 3185, 3187

Hydroxyl 3839

Isopropanol 226, 282, 321, 365, 420, 488, 844, 942, 965, 993, 1113, 1179, 1211, 1296, 1392, 1406, 1429, 1447, 1500, 1504, 1515, 1526, 3041, 3064, 3077, 3151, 3165, 3172, 3178, 3879

Nitrate ion 720, 720, 823, 1078, 1498, 1498

Propylene 196, 425, 576, 896, 942, 949, 1017, 1072, 1199, 1324, 1418, 1462, 1494, 1514, 1698, 3067, 3142, 3162, 3173, 3186, 3274

Water 1629, 3884, 4002

TS1 $-$ 600, 44, 55, 107, 134, 163, 181, 248, 263, 281, 360, 384, 439, 569, 738, 749, 807, 921, 956, 1004, 1030, 1082, 1136, 1174, 1204, 1349(2), 1376(604), 1405, 1436, 1482, 1495, 1501, 1512, 1662, 3063, 3072, 3160, 3163, 3189, 3196, 3346, 3842

TS2 $-$ 1101, 36, 54, 94, 115, 130, 225, 258, 292, 402, 429, 450, 562, 574, 619, 745, 773, 875, 914, 949, 964, 986, 1118, 1146, 1232, 1308, 1349, 1387, 1395, 1447, 1460, 1496, 1510, 1654, 1766, 3018, 3050, 3079, 3122, 3138, 3158, 3872

TS3 $-$ 1154, 50, 72, 102, 116, 140, 224, 259, 289, 399, 440, 453, 530, 573, 638, 720, 775, 843, 892, 931, 960, 977, 1078, 1191, 1245, 1301, 1368, 1375, 1414, 1444, 1481, 1509, 1519, 1644, 1744, 3062, 3064, 3124, 3140, 3159, 3168, 3878

TS4 $-$ 1107, 56, 67, 87, 123, 202, 225, 248, 324, 385, 415, 472, 552, 582, 640, 742, 774, 858, 903, 949, 960, 982, 1112, 1163, 1218, 1308, 1354, 1396, 1414, 1452, 1466, 1509, 1516, 1653, 1755, 3035, 3058, 3064, 3105, 3151, 3171, 3875

3.2 Solvation effect

	Frequencies (cm ${}^{-1}$ )
Isopropyl nitrate	77, 107, 209, 221, 273, 330, 416, 461, 578, 729, 760, 860, 895, 950, 966, 980, 1155, 1195, 1221, 1303, 1371, 1404, 1425, 1435, 1497, 1502, 1516, 1529, 1841, 3080, 3083, 3129, 3169, 3177, 3185, 3187
Hydroxyl	3839
Isopropanol	226, 282, 321, 365, 420, 488, 844, 942, 965, 993, 1113, 1179, 1211, 1296, 1392, 1406, 1429, 1447, 1500, 1504, 1515, 1526, 3041, 3064, 3077, 3151, 3165, 3172, 3178, 3879
Nitrate ion	720, 720, 823, 1078, 1498, 1498
Propylene	196, 425, 576, 896, 942, 949, 1017, 1072, 1199, 1324, 1418, 1462, 1494, 1514, 1698, 3067, 3142, 3162, 3173, 3186, 3274
Water	1629, 3884, 4002
TS1	$-$ 600, 44, 55, 107, 134, 163, 181, 248, 263, 281, 360, 384, 439, 569, 738, 749, 807, 921, 956, 1004, 1030, 1082, 1136, 1174, 1204, 1349(2), 1376(604), 1405, 1436, 1482, 1495, 1501, 1512, 1662, 3063, 3072, 3160, 3163, 3189, 3196, 3346, 3842
TS2	$-$ 1101, 36, 54, 94, 115, 130, 225, 258, 292, 402, 429, 450, 562, 574, 619, 745, 773, 875, 914, 949, 964, 986, 1118, 1146, 1232, 1308, 1349, 1387, 1395, 1447, 1460, 1496, 1510, 1654, 1766, 3018, 3050, 3079, 3122, 3138, 3158, 3872
TS3	$-$ 1154, 50, 72, 102, 116, 140, 224, 259, 289, 399, 440, 453, 530, 573, 638, 720, 775, 843, 892, 931, 960, 977, 1078, 1191, 1245, 1301, 1368, 1375, 1414, 1444, 1481, 1509, 1519, 1644, 1744, 3062, 3064, 3124, 3140, 3159, 3168, 3878
TS4	$-$ 1107, 56, 67, 87, 123, 202, 225, 248, 324, 385, 415, 472, 552, 582, 640, 742, 774, 858, 903, 949, 960, 982, 1112, 1163, 1218, 1308, 1354, 1396, 1414, 1452, 1466, 1509, 1516, 1653, 1755, 3035, 3058, 3064, 3105, 3151, 3171, 3875

However, alkaline hydrolysis reaction is carried out in solution actually. The characteristics of molecules and transition states in solution are quite different from that in standard state. Solvent can affect the reaction rate and the position of chemical equilibrium [23, 24, 25]. As a result, the solvation effect should be considered.

Table 2 shows the thermodynamic parameters including structure energy $E$ , zero-point energy (ZPE) and enthalpy $H$ of all reactants and products calculated at MP2/6-311 $+$ g(d,p) level in standard state and solution state.

Table 2
Thermodynamic parameters of all reactants and products in standard state and solution state

	$E$ /hartree		ZPE/Kcal		$H$ /hartree
	Standard state	Solvation	Standard state	Solvation	Standard state	Solvation
Isopropyl nitrate	$-$ 397.911303	$-$ 397.916722	0.112121	0.111998	$-$ 397.911304	$-$ 397.916722
Hydroxyl	$-$ 75.640014	$-$ 75.771724	0.008743	0.008816	$-$ 75.640014	$-$ 75.771724
Isopropanol	$-$ 193.8472949	$-$ 193.852949	0.109560	0.109275	$-$ 193.847295	$-$ 193.852949
Nitrate ion	$-$ 279.800066	$-$ 279.897851	0.014436	0.014270	$-$ 279.800066	$-$ 279.897851
Propylene	$-$ 117.546247	$-$ 117.547594	0.080162	0.079996	$-$ 117.546248	$-$ 117.547594
Water	$-$ 76.274720	$-$ 76.282752	0.021676	0.021580	$-$ 76.274721	$-$ 76.282752

Figure 3.

The reaction potential energy curves in standard state and solvation (s).

By observing Table 2, it is found that the thermodynamic parameters of all reactants and products in solution state are a bit lower than that in standard state.

Figure 3 describes the potential energy curves of the alkaline hydrolysis reaction obtained at the MP2/6-311 $+$ g(d,p) level in standard state and solution state.

As seen in Fig. 3, the process reactants forms complex 1 has no energy barrier in standard state. The energy of complex 1 is lower than that of reactants. Then complex 1 needs to overcome energy barrier to form transition state. The process transition state forms complex 2 also has no energy barrier. At last complex 2 overcomes energy barrier to form products. The energy sequence in salvation state is almost the same as that in standard state. The difference is that the energy of complex 1 in salvation state is nearly the same as the energy of reactants.

By analyzing the reaction potential energy curves, it is found that pathway 3(s) has the lowest energy barrier in eight calculation results, which is 14.34 Kcal/mol. In standard state, pathway 2 has the highest energy barrier. In solvation calculation results, pathway 1(s) has highest energy barrier, which is 19.77 Kcal/mol. This means that the reaction is easy to occur in the direction of pathway 3(s) at low temperature. Secondly, compared with the product energy, the product energy of pathway 1(s) is the lowest, which means that the reaction tends to pathway 1(s) direction at high temperature, and forms stable products, isopropanol, nitrate ion and water. At last, it is found that the reaction potential energy in solution state is much lower than that in standard state. The reaction potential energy difference is about 80 Kcal/mol.

The activation energy of R1 calculated by Gong et al. [12] with AM1 method was 18.10 Kcal/mol in standard state. Liu et al. [13] found that the activation energy of R1 was 12.55 Kcal/mol by DFT method in standard state. Wang and Xiao [14] used MINDO/3 method to calculate the activation energy of the S ${}_{\rm N}$ 2 reaction for five kinds of alkyl nitrates including methyl nitrate, ethyl nitrate, isopropyl nitrate, propyl nitrate and butyl nitrate. The activation energies are respectively 1.36, 6.31, 11.35, 5.26, 14.09 Kcal/mol. The activation energy of isopropyl nitrate hydrolysis reaction in Wang’s calculation results is consistent with Liu’s result, which are smaller than Gong’s result. The calculation result of standard state in this paper is different from the literature values. But the result of salvation is consistent with Gong’s result. At the same time, the activation energy in solution state is a bit higher than Liu and Wang’s results.

4. Conclusion

The alkaline hydrolysis reaction of isopropyl nitrate is investigated theoretically. Four reaction pathways are discussed. The salvation calculation results show that the reaction tends to form isopropanol and nitrate ion at high temperature.

The treatment of isopropyl nitrate is an urgent problem for national defense industry at present. However, there is still no related experiment research about the hydrolysis reaction of isopropyl nitrate or other treatment methods. The calculation results can be useful for further research of isopropyl nitrate hydrolysis reaction. The work done by this paper can provide theoretical guidance for the hydrolysis reaction experiment and environmental treatment of isopropyl nitrate.

Footnotes

Acknowledgments

We would like to thank South China Normal University for the provision of Gaussain 09 program. Thank Professor Wang Chaoyang for his guidance during the research.

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Quantum chemistry calculation for isopropyl nitrate hydrolysis reaction

Abstract

Keywords

1. Introduction

3. Results and discussion

3.1 Reaction mechanism

Table 2 Thermodynamic parameters of all reactants and products in standard state and solution state

Footnotes

Acknowledgments

References

Table 2
Thermodynamic parameters of all reactants and products in standard state and solution state