Correlation between Shock Sensitivity of Nitramine Energetic Compounds based on Small‐scale Gap Test and Their Electric Spark Sensitivity

Electric spark sensitivity and shock sensitivity based small‐scale gap test for nitramine energetic compounds are two important sensitivity parameters, which are needed for assessment of their safety in working places. A novel method is introduced for reliable prediction of electric spark or shock sensitivity of a desired nitramine energetic compound when reliable data for one of the sensitivity is available. A novel correlation with a high value of correlation coefficient (R² = 0.998) is derived between electric spark and shock sensitivities of 20 cyclic and acyclic nitramines. For these nitramines, the predicted results of electric spark sensitivities of the novel model are compared with two of the best available models. The root‐mean‐square (rms) and maximum deviations of the new model are 0.20 and 0.51 J, respectively, which are much less than two comparative methods. The reliability of the new method for prediction of electric spark sensitivity of further 14 nitramines is also compared with one of the best available methods, where the measured electric spark or shock sensitivities were not available in literature.     

New Correlation between Electric Spark and Impact Sensitivities of Nitramine Energetic Compounds for Assessment of Their Safety

Electric spark and impact sensitivities of nitramine energetic compounds are two important sensitivity parameters, which are closely related to many accidents in working places. For nitramines, in contrast to electric spark sensitivity, their impact sensitivity can be easily measured or predicted by various methods. A new approach is introduced to correlate electric spark and impact sensitivities of nitramine energetic compounds by the use of three structural parameters. The predicted results of the novel model for 20 nitramines are compared with two of the best available models, which are based on complex quantum mechanical approach and the measured values of activation energies of thermolysis. The root‐mean‐square (rms) and maximum deviations of the new model are 1.06 and 2.41 J, respectively. For further 14 nitramines, where the measured electric spark or impact sensitivities were not available, the estimated electric spark sensitivities by the new model are close to those predicted based on experimental data of activation energies of thermolysis.     

On the molecular origin of the sensitivity to impact of cyclic nitramines

Nitramine explosives can combine relative insensitivity to initiation and great energy content. In this work, based on a previous approach developed for nitroaromatic explosives, we propose four mathematical models to correlate impact sensitivity, given by the h₅₀ value, to molecular charge properties. Fourteen cyclic nitramines were studied using Density Functional Theory (DFT). Six molecules of the set have measured h₅₀ values, which were used to evaluate the sensitivity models. Converged DFT charge densities of the molecules were partitioned and analyzed according to the distributed multipole analysis (DMA) atom-centered method. The sensitivity models were based on the DMA electric multipole values. The electron withdrawing role of the nitro group and the strong polarization of the charges of the nitrogen atom in the amine group were clearly identified. The influence of the electronic properties on the sensitivity of the explosives was characterized by including in the sensitivity models the charge values of the nitro or the nitramine groups and electron delocalization, the latter quantified by the DMA quadrupole values of the ring atoms. Inclusion of electron delocalization effects can improve the prediction of h₅₀ values for two out of the five strained-ring nitramines in the set. The charge values of the nitramine groups are the most important molecular property affecting the impact sensitivity. The h₅₀ values of eight nitramine explosives of the set not available experimentally were computed.     

C_4H_4N_8O_(14)的晶体与分子结构

C_4H_4N_8O_(14)的晶体属单斜晶系,空间群P2_1/n。晶胞参数为:a=11.820,b=6.162,c=18.229,β=96.1°,Z=4,在PW1100四圆衍射仪上收集到I>2σ(Ⅰ)的衍射点2024个。晶体结构以自编的直接法计算程序解出,最后偏离因子R=0.105。     

In Situ Fabrication of Noble Metal Nanoparticles Modified Multiwalled Carbon Nanotubes and Related Electrocatalysis

Using multiwalled carbon nanotubes (MWNTs) as templates, noble metal (Au, Ag, Pt or Pd) nanoparticles (NPs) were fabricated in situ by electrochemistry with a diameter of 40–60 nm. Further, catalytic behaviors of these composite materials were investigated. Experiments showed that such carbon nanotubes decorated with Pd NPs modified glassy carbon electrodes exhibited higher electrocatalytic ability to some molecules such as evolution of hydrogen, reduction of oxygen and oxidation of ascorbic acid. Atomic force microscopy, X‐ray photoelectron spectroscopy and cyclic voltammetry were used to characterize the film formation and their properties.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

Density functional theory studies of effects of boron replacement on the structure and property of RDX and HMX

In this study, based on two model nitramine compounds hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5, 7-tetrazocine (HMX), two series of new energetic molecules were designed by replacing carbon atoms in the ring with different amounts of boron atoms, their structures and performances were investigated theoretically by the density functional theory method. The results showed that the boron replacement could affect the molecular shape and electronic structure of RDX and HMX greatly, and then would do harm to the main performance like the heat of formation, density, and sensitivity. However, the compound RDX-B2 is an exception; it was formed by replacing two boron atoms into the system of RDX and has the symmetric boat-like structure. Its oxygen balance (4.9%), density (1.91 g/cm³), detonation velocity (8.85 km/s), and detonation pressure (36.9 GPa) are all higher than RDX. Furthermore, RDX-B2 has shorter and stronger N NO₂ bonds than RDX, making it possesses lower sensitivity (45 cm) and better thermal stability (the bond dissociation energy for the N NO₂ bond is 204.7 kJ/mol) than RDX. Besides, RDX-B1 and HMX-B4 also have good overall performance; these three new molecules may be regarded as a new potential candidate for high energy density compounds.     

Detection of C,H, N,and O in capillary gas chromatography by atomic emission

Using a new atomic emission detector for gas chromatography, the quantitative and qualitative aspects of selective elemental detection of carbon, hydrogen, nitrogen, and oxygen were investigated. Sensitivity, precision, degree of tailing, and response variation between compounds are reported for capillary applications. Earlier atomic emission detectors reported poor sensitivity and selectivity for the analysis of oxygen. These problems have been greatly reduced due to lower interactions between elements in the sample and the silica wall of the water-cooled discharge tube. Using near-optimal sample amounts and chromatographic conditions, area precision was found to be very good with little variation in response factors among different compounds. For the compounds tested, response factors varied over a span of 2% to 3% for carbon, hydrogen, and nitrogen, and over 7% for oxygen. For quantitative analysis, area ratios were calibrated directly from the area ratios of two elements of an internal standard, and yielded better precision and compound independence than the individual calibrated response of each element. Empirical formulas were calcualted using one peak as a qualitative internal standard. Unambiguous formulas were determined for some, but not all, of the compounds tested. Further increases in precision and/or compound independence is needed before empirical formula determination can be used as a routine tool.     

X-ray crystallographic investigation of the adduct of decachloro-o-carborane with dimethyl sulfoxide

Conclusions The structure of the 11 adduct of decachloro-o-carborane with DMSO was determined by x-ray crystallography. It was established that the structure contains cyclic associates of two DMSO molecules and two decachloro-o-carborane molecules linked by hydrogen bonds of the C-H...O type.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2257–2261, October, 1982.     

Relation between Electric Spark Sensitivity and Impact Sensitivity of Nitroaromatic Energetic Compounds

Impact and electric spark sensitivities of energetic compounds are two important sensitivity parameters, which are closely related to many accidents in working places. In contrast to electric spark sensitivity, impact sensitivity can be easily measured. A new simple method is introduced to correlate electric spark and impact sensitivities of nitroaromatic compounds. Two correcting functions are used to consider several molecular moieties for reliable prediction of electric spark sensitivity through the measured or estimated impact sensitivity of nitroaromatics. The model is optimized using a set of 28 CHNO polynitroaromatic explosives and then it is tested for some nitroaromatics containing the other atoms such as sulfur. The predicted electric sensitivities of the new method are also compared with the reported results of a new quantum mechanical approach. For 22 CHNO nitroaromatics, quantum mechanical calculations are within ±3.0 J of 18 measured values and more than ±3.0 J for remaining 4 experimental data. Meanwhile, the predicted results of the method are less than ±3.0 J for 28 CHNO nitroaromatics. The root‐mean‐square (rms) deviations of the new model and quantum mechanical are also 1.55 and 2.51 J, respectively.     

Initiation and control of catalytic surface reactions with shaped femtosecond laser pulses

We report on femtosecond laser-induced catalytic reactions of carbon monoxide and hydrogen on single crystal surfaces under high vacuum conditions. Several product molecules are synthesized, among them also species for whose formation at least three reactants are required. By applying closed-loop optimal control, we manipulate these reactions and selectively optimize the ratio of different bond-forming reaction channels, in contrast to previous quantum control experiments aiming at bond-cleavage. Further experiments explore the nontrivial control mechanism and its sensitivity to the relative proportion of the two reactant gases.     

On the formation of ozone in oxygen-rich solar system ices via ionizing radiation

The irradiation of pure molecular oxygen (O(2)) and carbon dioxide (CO(2)) ices with 5 keV H(+) and He(+) ions was investigated experimentally to simulate the chemical processing of oxygen rich planetary and interstellar surfaces by exposure to galactic cosmic ray (GCR), solar wind, and magnetospheric particles. Deposited at 12 K under ultra-high vacuum conditions (UHV), the irradiated condensates were monitored on-line and in situ in the solid-state by Fourier transform infrared spectroscopy (FTIR), revealing the formation of ozone (O(3)) in irradiated oxygen ice; and ozone, carbon monoxide (CO), and cyclic carbon trioxide (c-CO(3)) in irradiated carbon dioxide. In addition to these irradiation products, evolution of gas-phase molecular hydrogen (H(2)), atomic helium (He) and molecular oxygen (O(2)) were identified in the subliming oxygen and carbon dioxide condensates by quadrupole mass spectrometry (QMS). Temporal abundances of the oxygen and carbon dioxide precursors and the observed molecular products were compiled over the irradiation period to develop reaction schemes unfolding in the ices. These reactions were observed to be dependent on the generation of atomic oxygen (O) by the homolytic dissociation of molecular oxygen induced by electronic, S(e), and nuclear, S(n), interaction with the impinging ions. In addition, the destruction of the ozone and carbon trioxide products back to the molecular oxygen and carbon dioxide precursors was promoted over an extended period of ion bombardment. Finally, destruction and formation yields were calculated and compared between irradiation sources (including 5 keV electrons) which showed a surprising correlation between the molecular yields (～10(-3)-10(-4) molecules eV(-1)) created by H(+) and He(+) impacts. However, energy transfer by isoenergetic, fast electrons typically generated ten times more product molecules per electron volt (～10(-2)-10(-3) molecules eV(-1)) than exposure to the ions. Implications of these findings to Solar System chemistry are also discussed.     

射频放电等离子体中CO2及CO2-H2混合气转化反应的原位研究

Currently, worldwide attention is focused on controlling the continually increasing emissions of greenhouse gases, especially carbon dioxide. To this end, a number of investigations have been carried out to convert the carbon dioxide molecules into value-added chemicals. As carbon dioxide is thermodynamically stable, it is necessary to develop an efficient carbon dioxide utilization method for future scaled-up applications. Recently, several approaches, such as electrocatalysis, thermolysis, and non-thermal plasma, have been utilized to achieve carbon dioxide conversion. Among them, non-thermal plasma, which contains chemically active species such as high-energy electrons, ions, atoms, and excited gas molecules, has the potential to achieve high energy efficiency without catalysts near room temperature. Here, we used radio-frequency (RF) discharge plasma, which exhibits the non-thermal feature, to explore the decomposition behavior of carbon dioxide in non-thermal plasma. We studied the ionization and decomposition behaviors of CO₂ and CO₂-H₂ mixtures in plasma at low gas pressure. The non-thermal plasma was realized by our custom-made inductively coupled RF plasma research system. The reaction products were analyzed by on-line quadrupole mass spectrometry (differentially pumped), while the plasma status was monitored using an in situ real-time optical emission spectrometer. Plasma parameters (such as the electron temperature and ion density), which can be tuned by utilizing different discharge conditions, played significant roles in the carbon dioxide dissociation process in non-thermal plasma. In this study, the conversion ratio and energy efficiency of pure carbon dioxide plasma were investigated at different values of power supply and gas flow. Subsequently, the effect of H₂ on CO₂ decomposition was studied with varying H₂ contents. Results showed that the carbon dioxide molecules were rapidly ionized and partially decomposed into CO and oxygen in the RF field. With increasing RF power, the conversion ratio of carbon dioxide increased, while the energy efficiency decreased. A maximum conversion ratio of 77.6% was achieved. It was found that the addition of hydrogen could substantially reduce the time required to attain the equilibrium of the carbon dioxide decomposition reaction. With increasing H₂ content, the conversion ratio of CO₂ decreased initially and then increased. The ionization state of H₂ and the consumption of oxygen owing to CO₂ decomposition were the main reasons for the V-shape plot of the CO₂ conversion ratio. In summary, this study investigates the influence of power supply, feed gas flow, and added hydrogen gas content, on the carbon dioxide decomposition behavior in non-thermal RF discharge plasma.     

Method d'estimation des limites d'inflammabilite

We have employed the criteria defined by the CHETAH (ASTM) program to predict the lower and the upper flammability limits of various organic compounds. The results obtained for molecules containing carbon, hydrogen, oxygen and nitrogen are, in most cases, in good agreement with experimental values. The difficulties encountered when the molecule contains a heteroatom can be overcome by knowledge of the stoichiometric conditions of the combustion reactions.     

A Theoretical Study of the Interaction of Hydrogen and Oxygen with Palladium or Gold Adsorbed on Pyridine‐Like Nitrogen‐Doped Graphene

The interaction of H₂ and O₂ molecules in the presence of nitrogen‐doped graphene decorated with either a palladium or gold atom was investigated by using density functional theory. It was found that two hydrogen molecules were adsorbed on the palladium atom. The interaction of these adsorbed hydrogen molecules with two oxygen molecules generates two hydrogen peroxide molecules first through a Eley–Rideal mechanism and then through a Langmuir–Hinshelwood mechanism. The barrier energies for this reaction were small; therefore, we expect that this process may occur spontaneously at room temperature. In the case of gold, a single hydrogen molecule is adsorbed and dissociated on the metal atom. The interaction of the dissociated hydrogen molecule on the surface with one oxygen molecule generates a water molecule. The competitive adsorption between oxygen and hydrogen molecules slightly favors oxygen adsorption.     

Characterization of a microelectromechanical systems-based counter-current flame ionization detector

This work is concerned with the influence of different operating parameters on the response of a counter-current micro flame ionization detector (cc-μFID) with low gas consumption for mobile applications. At cc-μFID flow rates (<10ml/min hydrogen), the response depends mainly on the oxygen flow. At 7.5ml/min hydrogen flow, highest sensitivity (13.7mC/gC) is obtained with the smallest flame chamber and nozzle size, moderate sample gas flow (2.0ml/min), and an oxygen flow above stoichiometry (9.4ml/min, λ=2.5). The largest absolute signal is obtained at increased sample gas flow (8.0ml/min). However, to prevent parting of the micro-flame by the sample gas stream, largest nozzles (smallest outflow velocity) give the best result (4.37nA). Whereas cc-μFID sensitivity is comparable with conventional FID sensitivity, peak-to-peak noise of 1pA is relatively large. Therefore, the minimum detectable carbon mass flow of 1.46×10(-10)gC/s and the minimum detectable methane concentration of 3.43ppm are larger than typical FID detection limits. μGC-μFID experiments show the difference between premixing the sample with the hydrogen or with the oxygen with respect to sensitivity and response factors. Sensitivity is decreased considerably when the column effluent is added to the oxygen instead of to the hydrogen. For hydrogen premixed samples the response factor to butane can be increased up to 0.81 (methane=1), whereas for oxygen premixed samples it is maximally 0.31. This smaller sensitivity to oxygen premixed samples and the larger variation of response factors shows the importance of the hydrogen atom during breakdown of organic molecules to single-carbon fragments before ionization.     

Infrared spectroscopy of acetone-water liquid mixtures. II. Molecular model

In aqueous acetone solutions, the strong bathochromic shifts observed on the OH and CO stretch infrared (IR) bands are due to hydrogen bonds between these groups. These shifts were evaluated by factor analysis (FA) that separated the band components from which five water and five acetone principal factors were retrieved [J. Chem. Phys. 119, 5632 (2003)]. However, these factors were abstract making them difficult to interpret. To render them real an organization model of molecules is here developed whose abundances are compared to the experimental ones. The model considers that the molecules are randomly organized limited by the hydrogen bond network formed between the water hydrogen atoms and the acetone or water oxygen atoms, indifferently. Because the oxygen of water has two covalent hydrogen atoms which are hydrogen-bonded and may receive up to two hydrogen atoms from neighbor molecules hydrogen-bonded to it, three types of water molecules are found: OH2, OH3, and OH4 (covalent and hydrogen bonds). In the OH stretch region these molecules generate three absorption regimes composed of nu3, nu1, and their satellites. The strength of the H-bond given increases with the number of H-bonds accepted by the oxygen atom of the water H-bond donor, producing nine water situations. Since FA cannot separate those species that evolve concomitantly the nine water situations are regrouped into five factors, the abundance of which compared exactly to that retrieved by FA. From the factors' real spectra the OH stretch absorption are simulated to, respectively, give for the nu3 and nu1 components the mean values for OH2, 3608, 3508; OH3, 3473, 3282 and OH4, 3391, 3223 cm(-1). The mean separations from the gas-phase position which are respectively about 150, 330, and 400 cm(-1) are related to the vacancy of the oxygen electron doublets: two, one, and zero, respectively. No acetone hydrate that sequesters water molecules is formed. Similarly, acetone produces ten species, two of which evolve concomitantly. Spectral similarities further reduce these to five principal IR factors, the abundance of which compared adequately to the experimental results obtained from FA. The band assignment of the five-acetone spectra is given.     

高分子聚合物-多壁碳纳米管复合物固定漆酶及其在玻碳电极上的直接电子迁移

采用不同结构的高分子聚合物与纯化的多壁碳纳米管(MWCNTs)共混的方法,制备得到聚合物非共价功能化多壁碳管复合物,测定了这些载体对漆酶(lac)的担载量、固定漆酶的比活力及稳定性.以固定漆酶的复合物修饰玻碳(GC)电极后,采用循环伏安法研究这些电极在无氧磷酸盐缓冲液(PBS)中的直接电化学行为及催化氧还原活力,粗略地测定了固定漆酶与电极间电子转移的速率常数.实验结果表明,当聚合物中含亲漆酶基团或能与漆酶活性中心发生相互作用的官能团时利于直接电子转移,而且复合物固定漆酶保持了游离漆酶的天然构象.这些电极中,lac/NIPAM-co-BPCP-M WCNTs/GC(NIPAM-co-BPCP:N-烯丙基-1-苯甲酰基-3-苯基-4,5-2H-4-甲酰胺基吡唑-co-N-异丙基丙烯酰胺)在无氧PBS中发生直接电子转移的式电位(605mV)更接近漆酶活性中心的式电位(580mV),具有较快的异相电子转移速率(0.726s-1),较高的漆酶担载量(103.5mg/g)和固定漆酶比活力(1.68U/mg),较高的催化氧还原能力(氧还原起始电位820mV,在650mV时的催化峰电流为85.5μA)以及良好的重复使用性和长期使用性.     

An unusual pathway for the elimination of hydrogen cyanide from benzonitrile upon electron impact as revealed by 13C and 15N labelling

It is shown by ¹⁵N and specific ¹³C labelling that ～50% of the molecules of hydrogen cyanide, eliminated within ～10^?6 s upon electron impact of benzonitrile, contains the original cyano carbon atom, whereas the remaining percentage contains one of the phenyl ring carbon atoms at random. This is even more dramatic for the molecular ions of benzonitrile which decompose in the first and second field-free regions of the VG Micromass ZAB-2F high-field mass spectrometer used. Then only 5–7% of the eliminated molecules of hydrogen cyanide contains the original cyano carbon atom. A cycloaddition-cycloreversion process in the molecular ions, leading to ionized 1-cyano-1,3-hexadien-5-yne as an intermediate in the hydrogen cyanide loss, is proposed to explain this.     

Raman studies of hydrogen adsorbed on nanostructured porous materials

Raman spectroscopy was applied to study the adsorbed hydrogen phase in porous materials at room temperature and under cryogenic conditions. A comparison between the Raman spectra of H(2) molecules adsorbed on single walled carbon nanotubes and on a Cu-based metal-organic framework reveals that the interaction strength for the adsorption of molecular hydrogen is very similar in these materials. In both cases the small perturbation of the Raman spectrum of hydrogen indicates that adsorption takes place without any evident charge transfer between H(2) and the adsorbent. Additionally for single walled carbon nanotubes at least two types of adsorption sites could be identified by Raman spectroscopy.