Study of Plastic Explosives based on Attractive Cyclic Nitramines Part I. Detonation Characteristics of Explosives with PIB Binder

Four plastic explosives based on energetic nitramines and a non‐energetic binder were prepared and studied. The nitramines were RDX (1,3,5‐trinitro‐1,3,5‐triazine), HMX (1,3,5,7‐tetranitro‐1,3,5,7‐tetrazine), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20). The binder was in all cases polyisobutylene (PIB) as in the standard composition C‐4. These powerful plastic explosives were compared to standard PETN‐based commercially available explosives Semtex 1A and Sprängdeg m/46. The detonation velocities were experimentally measured and compared to the ones calculated by the Kamlet–Jacobs method, CHEETAH and EXPLO5 Codes. The experimental detonation velocities as well as the calculated detonation parameters decrease in the following order: HNIW‐PIB>HMX‐PIB≥BCHMX‐PIB>RDX‐PIB>Sprändeg m/46≥Semtex 1A. Urizar coefficients for the various binders were calculated from experimental data.     

Study of Plastic Explosives based on Attractive Cyclic Nitramines,Part II. Detonation Characteristics of Explosives with Polyfluorinated Binders

A series of plastic bonded explosives (PBXs) based on Viton A and Fluorel binders were prepared using four nitramines, namely RDX (1,3,5‐trinitro‐1,3,5‐triazinane), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole), and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane). The detonation velocities, D, were determined. Detonation parameters were also calculated by means of modified Kamlet & Jacobs method, CHEETAH and EXPLO5 codes. In accordance with our expectations BCHMX based PBXs performed better than RDX based ones. The Urizar coefficient for Fuorel binder was also calculated.     

Attractive Nitramines and Related PBXs

At present, cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole (bicyclo‐HMX, BCHMX) and ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane (ε‐HNIW, CL‐20) are a topic of interest from the attractive and the potentially attainable nitramines. They were chosen to be studied in comparison with 1,3,5‐trinitro‐1,3,5‐triazinane (RDX) and β‐1,3,5,7‐tetranitro‐1,3,5‐tetrazocane (β‐HMX). Marginal attention is devoted also to 4,8,10,12‐tetranitro‐2,6‐dioxa‐tetraazawurtzitane (Aurora 5). BCHMX, ε‐HNIW, RDX, and HMX were studied as plastic bonded explosives (PBXs) with elastic properties based on Composition C4 and Semtex 10 matrices. Also they were studied as a highly pressed PBXs based on the Viton A binder. The detonation parameters and sensitivity aspects of these nitramines and their corresponding PBXs were determined. Relative explosive strengths (RS) of these compositions are mentioned with mutual relationships between the measured RS values and some detonation parameters. These relationships indicate a possibility of changes in detonation chemistry of these mixtures filled mainly by HNIW. A sensitivity of RS‐CL20 (HNIW with reduced sensitivity) is reported and the new findings in the friction sensitivity are discussed.     

Effect of Different Polymeric Matrices on Some Properties of Plastic Bonded Explosives

Matrices based on polyisobutylene (PIB), polymethyl‐methacrylate (PA), Viton A 200, Dyneon FT 2481 (Fluorel), and polydimethyl‐siloxane binders were studied as desensitizers. A series of plastic explosives (PBXs) were prepared, based on four different nitramines, namely RDX (1,3,5‐trinitro‐1,3,5‐triazinane), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20), bonded by the matrices mentioned. For comparison, pentaerythritol tetranitrate and certain commercial explosives based on it, Semtex 1A, Semtex 10 and Sprängdeg m/46, were used. Detonation velocities, sensitivities to impact and friction, and peak temperatures of thermal decomposition by differential thermal analysis technique (DTA) for all the explosives studied were determined. Heat of detonation was calculated by means of a thermodynamic calculation program (EXPLO 5 code). Fluoroelastomers have a neutral to positive effect on the thermal stability of nitramines and they have a significant effect on decreasing the friction sensitivity. However, their anti‐impact efficiency is the lowest in this study although they have a positive effect on performance of the corresponding PBXs. PA and PIB matrices markedly decrease thermal stability of nitramines, the anti‐impact influences of PIB‐binders are better than those of PA‐binders, while PA‐binders have a higher anti‐friction effect and slightly less negative influence on the performance of the PBXs in comparison with PIB mixtures. The polydimethyl‐siloxane matrix has a neutral effect on thermal stability of the nitramines studied, it has an influence on the volume thermochemistry of detonation comparable with that of fluoroelastomers although it does not provide comparable performance, and its corresponding PBXs have optimum sensitivity parameters.     

Explosive Strength and Impact Sensitivity of Several PBXs Based on Attractive Cyclic Nitramines

Plastic explosives based on different cyclic nitramines with different polymeric matrices were prepared and studied. The used polymeric matrices were fabricated on the basis of polyisobutylene (PIB), acrylonitrile‐butadiene rubber (ABR), Viton A, and polydimethyl‐siloxane as binders, whereas the nitramines named RDX (1,3,5‐trinitroperhydro‐1,3,5‐triazine), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine), BCHMX (cis‐1,3,4,6‐tetranitrooctahydroimidazo‐[4,5‐d]imidazole) and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane) were used as explosive fillers. Commercial Semtex 10, based on pentaerythritol tetranitrate (PETN), was used for comparison. Impact sensitivity, loading density, ρ, detonation velocity, D, and relative explosive strength (RS) measured by ballistic mortar were determined. It was concluded that plastic BCHMX based on Viton A or PIB‐matrix exhibits higher RS compared with PBXs based on RDX and HMX. Correlations between RS and the impact sensitivity, the ρD² term and the square of the detonation velocity were studied and discussed. The results confirm the well‐known fact that increasing the performance is usually accompanied by an increase in the sensitivity of the explosives. In this connection, Viton A enables achieving a high RS, but with a relatively high sensitivity of the PBXs, whereas the polydimethyl‐siloxane matrix should perhaps give PBXs with optimum explosive strength and sensitivity parameters.     

Degradation of TNT,RDX, and HMX Explosive Wastewaters Using Zero‐Valent Iron Nanoparticles

The high‐energy explosives 2,4,6‐trinitrotoluene (TNT), hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX), and the high melting explosive octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) are common groundwater contaminants at active and abandoned munitions production facilities causing serious environmental problems. A highly efficient and environmentally friendly method was developed for the treatment of the explosives‐contaminated wastewaters using zero‐valent iron nanoparticles (ZVINs). ZVINs with diameters of 20–50 nm and specific surface areas of 42.56 m² g⁻¹ were synthesized by the co‐precipitation method. The explosives degradation reaction is expressed to be of pseudo first‐order and the kinetic reaction parameters are calculated based on different initial concentrations of TNT, RDX, and HMX. In addition, by comparison of the field emission scanning electron microscopy (FE‐SEM) images for the fresh and reacted ZVINs, it was apparent that the ZVINs were oxidized and aggregated to form Fe₃O₄ nanoparticles as a result of the chemical reaction. The X‐ray diffraction (XRD) and X‐ray absorption near edge structure (XANES) measurements confirmed that the ZVINs corrosion primarily occurred due to the formation of Fe₃O₄. Furthermore, the postulated reaction kinetics in different concentrations of TNT, RDX, and HMX, showed that the rate of TNT removal was higher than RDX and HMX. Furthermore, by‐products obtained after degradation of TNT (long‐chain alkanes/methylamine) and RDX/HMX (formaldehyde/methanol/hydrazine/dimethyl hydrazine) were determined by LC/MS/MS, respectively. The high reaction rate and significant removal efficiencies suggest that ZVINs might be suitable and powerful materials for an in‐situ degradation of explosive polluted wastewaters.     

DFT Studies on a Series of Nitramines Containing Pyridine Ring

In this article, a series of nitramines containing pyridine ring were studied by density functional theory (DFT). The gas-phase heats of formation were predicted based on the isodesmic reactions and the condensed-phase heats of formation and heats of sublimation were estimated with the Politzer's approach. The detonation velocity and pressure were calculated using the empirical Kamlet-Jacobs equation. Many title compounds have better performance than RDX (hexahydro-1,3,5-trinitro-1,3,5-trizine) and HMX (1,3,5,7-tetranitro-1,3,5,7- tetraazacyclooctane). The impact sensitivity was evaluated with the characteristic height (h₅₀). It is found that most of the studied compounds have lower sensitivities than CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexaazaisowurtzitane). The crystal structures were predicted with the molecular mechanics method and optimized by the CA-PZ local density approximation of DFT. Analysis of the crystal energy gap indicates I-13, II-1, III-1, and IV-1 are nearly conductors and other compounds are semiconductors. For I-1～I-8 and I-11, the largest contribution to the valence bands is mainly from the p states of the C and N atoms in the pyridine and fused ring and for the other compounds, from the p states of the C and N atoms in the amino group and pyridine.     

Selective Extraction of N‐Heterocyclic Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) Using Molecularly Imprinted Polymers

N‐heterocyclic compounds are key nitration precursors for some high energy density explosives such as 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX). Nitration of 1,3,5,7‐tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) yields HMX in high yields and purity. However, the analogue 1,3,5‐triacetyl‐1,3,5‐triazacyclohexane (TRAT) is easily co‐produced via the condensation of acetonitrile and 1,3,5‐trioxan. To selectively extract TAT from a mixture of TAT and TRAT, the molecular imprinting technology (MIT) was developed in this study. The capacity of the dry polymer is 16 mg g⁻¹ and the recovery surpasses 75 %.     

Study of the Elaboration of HMX and HMX Composites by the Spray Flash Evaporation Process

The Spray Flash Evaporation (SFE) process invented and developed at the NS3E laboratory allows obtaining different nanosized explosives (TNT, RDX, CL‐20…). This process is based on the very fast evaporation of the solvent due to the drastic modification of pressure and temperature leading to the crystallization of the molecules present in solution into nanometric or submicrometric particles. Here, we show the possibility to prepare pure HMX (Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) or HMX based composites at the nanoscale using this process. This study mainly focuses on the size, morphology and crystallographic phases obtained for HMX and HMX/TNT composites depending on the experimental conditions (temperature, pressure, solution concentration…) used during the elaboration. For this purpose, the results obtained from scanning electron microscopy, X‐ray diffraction and Raman spectroscopy are discussed.     

Sensitivity and Performance of Energetic Materials

This paper provides an overview of the main developments over the past nine years in the study of the sensitivity of energetic materials (EM) to impact, shock, friction, electric spark, laser beams, and heat. Attention is also paid to performance and to its calculation methods. Summaries are provided of the relationships between sensitivity and performance, the best representations for the calculation methods of performance being the volume heat of explosion or the product of crystal density and the square of detonation velocity. On the basis of current knowledge, it is possible to state that a single universal relationship between molecular structure and initiation reactivity does not yet exist. It is confirmed that increasing the explosive strength is usually accompanied by an increase in the sensitivity. In the case of nitramines this rule is totally valid for friction sensitivity, but for impact sensitivity there are exceptions to the rule, and with 1,3,5‐trinitro‐1,3,5‐triazepane, 1,3,5‐trinitro‐1,3,5‐triazinane, β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane, and the α‐, β‐ and ε‐polymorphs of 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane the relationship works in the opposite direction. With respect to the QSPR approach there might be reasonably good predictions but it provides little insight into the physics and chemistry involved in the process of initiation.     

Energetic Characteristics of HMX‐Based Explosives Containing LiH

The high energy density compound octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) and the strong exothermic compound LiH represent an excellent principal explosive and an active fuel, respectively. Herein, the energetic characteristics of HMX‐based explosives are explored by adding LiH as fuel additive. The detonation parameters of HMX‐based explosives containing LiH were tested with free‐field explosion experiments and compared with those of traditional TNT, HMX, and aluminized explosives. The results show that the explosives exhibit higher energy and present preferable explosion effect when LiH is added as an explosive ingredient. The improvement of impulse is more than 32.8 % at 2 m. The shock wave peak overpressure increases by almost 40 % at a distance of 3 m from detonation center specially for the explosive containing both LiH and Al additives. Elemental H and Li are expected to release tremendous energy to effectively improve the explosives instant damage power, but the detonation duration is shorter than that of Al‐containing mixed explosives, which may limit the advantage over Al in the impulse. Li₂CO₃ powder is the solid product of HMX/LiH, which explains the LiH oxidation during the explosion. The exothermic processes in the formation are the reason for the increased energy of HMX/LiH explosives. These results can provide guidance to a potential energetic system formed by HMX and LiH.     

Quantum Chemical Studies on the Structure and Performance Properties of 1,3,4,5‐Tetranitropyrazole: A Stable New High Energy Density Molecule

Molecular orbital calculations were performed for the geometric and electronic structures, band gap, thermodynamic properties, density, detonation velocity, detonation pressure, stability and sensitivity of 1,3,4,5‐tetranitropyrazole ( R23 ). The calculated density (approx. 2060 kg m⁻³), detonation velocity (approx. 9.242 km s⁻¹) and detonation pressure (approx. 41.30 GPa) of the model compound are appearing to be promising compared to hexahydro‐1,3,5‐trinito‐1,3,5‐triazine (RDX) and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetrazocine (HMX). Bader’s atoms‐in‐molecules (AIM) analysis was also performed to understand the nature of the intramolecular N ⋅⋅⋅ O interactions and the strength of trigger X NO₂ bonds (where XC, N) of the optimized structure computed from the B3LYP/aug‐cc‐pVDZ level.     

Micro Videographic Analysis of the Melt Layer of Self‐Deflagrating HMX and RDX

Micro videographic analysis of the thin molten layer on the surface of HMX (Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) and RDX (Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine) during self deflagration were performed. This was done to gain a better understanding of the physical structure present in this 100–300 μm layer and give a visual picture for the development of computational models. During steady‐state combustion, RDX had a consistent melt layer with vigorous bubble formation. There was a continuous liquid layer throughout combustion and no foam was formed. The surface of HMX during steady‐state combustion at ambient initial temperatures was an uneven layer of foam. Foam appeared to convect across the surface in undulating waves. At elevated initial temperatures, the HMX molten layer was a consistent foam layer in both time and space. Micro videography was also done with a diagnostic laser sheet as illumination to measure the melt layer thickness. The RDX bubbling layer was about 217±30 μm thick. The HMX foam thickness varied from almost nothing to 660 μm, with an average value of about 234±106 μm.     

Analysis of Polar Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetrazocine (HMX) Using Hydrophilic Interaction Chromatography

Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) is currently one of the most widely used explosives. 1,3,5,7‐Tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) is an attractive precursor for the synthesis of HMX; the nitration of this key precursor results in both high yield and purity under mild condition. TAT can be prepared either by acetylation of 2,6‐diacetyl‐pentamethylenetetramine (DAPT) or by the condensation of ACN and 1,3,5‐trioxane. However, TAT and DAPT are polar compounds, and are difficult to analyze using reverse phase liquid chromatography. Herein, a chromatography method for the direct separation of these polar compounds was developed using hydrophilic interaction chromatography (HILIC) using a Venusil HILIC column, with ACN/water (95/5, v/v) as the mobile phase. The chromatographic analysis and identification of these polar compounds provide valuable information for the optimization of the synthetic process of TAT.     

Projectile Impact Ignition and Reaction Violent Mechanism for HMX‐Based Polymer Bonded Explosives at High Temperature

Determining the mechanism of transition from projectile‐impact ignition to detonation is a complex and difficult task with strong practical applications. Ignition due to low‐velocity projectile impact cannot be properly explained by the available theories. We attempted to determine the mechanisms of initiation of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX)‐based polymer‐bonded explosives (PBXs) in a range of high temperatures, which have rarely been investigated. Comparing the shock initiation results, we found that the low‐velocity projectile impact response mechanisms for a heated explosive are much more complex. Our results show that the impact ignition threshold velocity of the heated explosive does not always decrease with increasing temperature as commonly expected. A temperature dependent plastic power during impact controls the ignition in the range of 25 °C to 75 °C. At 190 °C and 200 °C, there was a sharp rise of reaction degree induced by β→δ phase transition for high HMX‐content PBX. Conversely, such phase transition effect becomes insignificant for low (<50 %) HMX‐content PBX. Our results show that three competing mechanisms affect the impact safety for a high HMX‐content PBX at high temperature, including plastic power, temperature sensitizing, and phase transition.     

High Speed Imaging of TATB‐ and HMX‐Based Energetic Material Decomposition in Molten Salts

Immersion of energetic materials into high‐temperature molten‐salt baths, where the energetic materials decompose, is being considered as a method for their safe destruction. In the present research, behaviors of the high explosives LX‐17 (92.5 wt% 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB), 7.5 wt% KeI‐F 800 plastic binder) and LX‐04 (85 wt% octahydro‐,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX), 15 wt% Viton A plastic hbinder) were studied when these materials were immersed into molten salt baths. Pressed cylindrical samples initially 6.35 mm in diameter and length were immersed in molten salt baths, and data were taken photographically. Sample decomposition behaviors were observed for varied salt temperatures in a molten LiCl‐NaCl‐KC1 eutectic and then separately in a molten Li₂CO₃‐Na₂CO₃‐K₂CO₃ eutectic. Bath temperatures ranged from 650 to 750°C. General combustion behaviors such as bubble formation characteristics, gas evolution, and sample lifetimes were observed. Results indicated that sample lifetimes decreased as bath temperatures increased, and that the carbonate eutectic increased initial decomposition rates and decreased sample lifetimes relative to the chloride eutectic.     

老化对TNT基熔铸炸药性能的影响

为了研究老化对炸药性能的影响,对自然贮存的3种熔铸炸药TNT／RDX、TNT／RDX／Al和 TNT／HMX／Al进行了加速老化试验。通过扫描电镜、真空安定性试验研究了老化前后3种炸药的微观形貌和安全性能,并测试了老化前后3种炸药的感度和爆速。结果表明,老化后炸药颜色变深,体积膨胀,质量变轻。样品的放气量小于2 mL／g ,热感度变化也较小。机械感度的变化与炸药组分和老化方式有关。TNT／RDX的爆速随着贮存时间的增加而降低,与整体加速老化情况一致,TNT／RDX／Al和 TNT／HMX／Al的爆热随贮存时间的增加变化趋势相反,说明两者老化机理可能不同。     

Thermal decomposition kinetics and compatibility of NH3OHN5

Hydroxylammonium cyclo-pentazolate (NH₃OHN₅), as one of the poly-nitrogen compounds, has a broad prospect in the field of energetic materials, due to its high specific impulse, high detonation velocity, and the pollution-free products. In this paper, the thermal decomposition behavior of NH₃OHN₅ was studied by differential scanning calorimetry (DSC) using four heating rates (2, 5, 8, 10 °C min⁻¹). The apparent activation energy (E_K,O=114.31 kJ mol⁻¹), the pre-exponential factor (A_K=4.78×10¹¹ s⁻¹) and the critical temperature of the thermal explosion (T_b=108.08 °C) of NH₃OHN₅ were calculated by Kissinger and Ozawa method under non-isothermal heating conditions. The compatibility of NH₃OHN₅ with 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaza-isowurtzitane (CL-20), ammonium perchlorate (AP), and hydroxy-terminated polybutadiene (HTPB) were tested and judged based on a standard agreement (STANAG-4147). The DSC results showed that NH₃OHN₅/HMX, NH₃OHN₅/RDX, NH₃OHN₅/CL-20, NH₃OHN₅/AP and NH₃OHN₅/HTPB had good compatibility.     

Analytical Characterization of Impurities or Byproducts in New Energetic Materials

In the last years several new explosives have recently attracted attention as possible alternatives, e.g. for the nitramines RDX and HMX. Hexanitrohexaazaisowurtzitane (HNIW) also known as CL 20 is one of them. Objective of the study was to analyse three different CL 20 samples from different suppliers (ϵ-CL 20 from Thiokol, USA and ϵ- and β-CL 20 from SNPE, France) with chromatographic and spectroscopic techniques to characterize the chemical and polymorph purity of the materials in order to compare the different samples to each other. From IR-spectroscopic measurements it was determined that all three materials have polymorph purities >95%. To get informations about the chemical purity and possible byproducts or residual solvents the samples were analysed by HPLC, NMR and GC-MSD. For the last a new technique, the so called Solid Phase Micro Extraction, SPME was applied for sample preparation. The chemical purity estimated by HPLC analysis was for all CL 20 samples >96% while the ϵ-charge of SNPE had the highest purity (98.3%). From NMR-measurements an acetyl- or formyl-substituted byproduct was identified. From NMR as well as from GC-MSD analyses residual amounts of organic solvents have been detected (ethanol or tetrahydrofuran). Furthermore different spare amounts of other organic components were identified after SPME-treatment and characterization with GC-MSD.     

Kinetic Deuterium Isotope Effects in the combustion of formulated nitramine propellants

The kinetic deuterium isotope effect was used to investigate the rate-limiting process in the combustion of formulated nitramine propellants. Model propellant formulations containing either octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), or their deuteriated analogues were pressed into pellets and burned under nitrogen pressure in a window bomb. The magnitudes of the observed deuterium isotope effects indicate that the HMX and RDX exert significant control over the combustion phenomenon of the propellants studied. Furthermore, assuming a consistent mechanism between decomposition and combustion, the observed isotope effects suggest that a carbon-hydrogen bond rupture in HMX or RDX is the rate-controlling step in the combustion of the model nitramine propellants. Observed isotope effect values for HMX-CW5 and RDX-CW5 formulated propellants at 1000 psig (6.99 MPa) pressure were 1.29 ± 0.09 and 1.24 ± 0.07, respectively, compared to a theoretical estimate of 1.29 for a primary effect due to C H bond rupture at 673 K.