Shocked hydrocarbons

High-pressure experiments promise to provide insight into chemical reactivity under extreme conditions. For instance, chemical equilibrium analysis of shocked hydrocarbons predicts the formation of condensed carbon and molecular hydrogen.17 Similar mechanisms are at play when detonating energetic materials form condensed carbon.10 Diamond anvil cell experiments have been used to determine the equation of state of methanol under high pressures.18 We can then use a thermodynamic model to estimate the amount of methanol formed under detonation conditions.19... 

Other workers [112, 113] have shown that a chemical equilibrium model of hydrocarbons based on an exponential-6 fluid model using Ross s soft-sphere perturbation theory is successful in reproducing the behavior of shocked hydrocarbons. Our model of the supercritical phase includes the species H2, CH4, C2H6, and C2H4. We have chosen model parameters to match both static compression isotherms and shock measurements wherever possible. The ability to match multiple types of experiments well increases confidence in the general applicability of our high-pressure equation of state model. 

Aluminum bromide and chloride are equally active catalysts, whereas boron trifluoride is considerably less active probably because of its limited solubiUty in aromatic hydrocarbons. The perchloryl aromatics are interesting compounds but must be handled with care because of their explosive nature and sensitivity to mechanical shock and local overheating. 

Stabilized lithium acetyhde is not pyrophoric or shock-sensitive as are the transition-metal acetyhdes. Among its uses are ethynylation of halogenated hydrocarbons to give long-chain acetylenes (132) and ethynylation of ketosteroids and other ketones in the pharmaceutical field to yield the respective ethynyl alcohols (133) (see Acetylene-derived chemicals). 

There are also a number of nonaerospace civiHan appHcations for this material. Small diaphragms have found limited use in automotive and related appHcations. These are used because of the material s exceUent fatigue life and hydrocarbon resistance. A compound containing methacrylates functions as a soft liner for dentures (16), providing extended life, shock isolation, and resistance to microbial attack. 

Another analogous series of unsaturated hydrocarbons that contain just one multiple bond, but, instead of being a double bond, it is a triple bond is the alkynes. The names of all the compounds end in -yne. The only compound m this series that is at all common happens to be an extremely hazardous material. It is a highly unstable (to heat, shock, and pressure), highly flammable gas that is the first compound in the series. This two-carbon unsaturated hydrocarbon with a triple bond between its two carbon atoms is called ethyne, and indeed this is its proper name. It is, however, known by its common name, acetylene. 

Chemical explosions are uniform or propagating explosions. An explosion in a vessel tends to be a uniform explosion, while an explosion in a long pipe is a propagating explosion. Explosions are deflagrations or detonations. In a deflagration, the burn is relatively slow, for hydrocarbon air mixtures the deflagration velocity is of the order of 1 m/s. In contrast, a detonation flame shock front is followed closely by a combustion wave that releases energy to sustain the shock wave. A... 

In a numerical exercise described in section 4.2.2, it was shown that, for a stoichiometric, hydrocarbon-air detonation, the theoretical maximum efficiency of conversion of heat of combustion into blast is equal to approximately 40%. If the blast energy of TNT is equal to the energy brought into the air as blast by a TNT detonation, a TNT equivalency of approximately 40% would be the theoretical upper limit for a gas explosion process under atmospheric conditions. However, the initial stages in the process of shock propagation in the immediate vicinity of... 

Detonation explosions are similar to combustion explosions and are exothermic reactions that proceed into the unreacted material at a velocity much greater than the speed of sound in an unreacted material and are accompanied by a flame front shock wave in the material followed closely by a combustion wave that releases the energy and sustains the shock wave at extremely high pressure [39] [40]. In hydrocarbons, the velocity can reach 6,000-9,000 ft/sec. 

These Dynamites were stable and fairly insensitive to shock. Incorporation of hydrocarbons rendered them still less sensitive, and suitable for military purposes... 

Hydrazinium diperchlorate (HP2) is one of the higher energetic oxidizers considered for use in composite solid propints with hydrocarbon binders. Its other advantages include high density, high burning rate, and moderate projected cost. Its shortcomings include relatively poor stability to vibrational and thermal shock... 

The above statements are adequate for liquid defoamers that are insoluble in the bulk. Experience has proven, however, that certain dispersed hydrophobic solids can greatly enhance the effectiveness of defoaming. A strong correlation between the effectiveness of a defoamer and the contact angle for silicone-treated silica in hydrocarbons has been established [300]. It is believed that the dewetting process of the hydrophobic silica causes the collapse of a foam by the direct mechanical shock occurring by this process. 

The liquid material in cylinders (which contains around 30% of propadiene) is not shock-sensitive, but a wall temperature of 95°C (even very localised) accompanied by pressures of about 3.5 bar, will cause a detonation to propagate from the hot spot [1]. Induced decomposition of the endothermic hydrocarbon leads to flame... 

This compound was found, on investigation of an explosion in a syringe during transfer, to have a decomposition energy equivalent to that of commercial explosives. Slow decomposition, even at room temperature, becomes explosive above 100°C. Shock sensitive. Stable as hydrocarbon solution below 25% concentration. Recommended that this and related compounds be handled only in such solution. See FLUORINATED ORGANOLITHIUM COMPOUND... 

The substantial effect of secondary breakup of droplets on the final droplet size distributions in sprays has been reported by many researchers, particularly for overheated hydrocarbon fuel sprays. 557 A quantitative analysis of the secondary breakup process must deal with the aerodynamic effects caused by the flow around each individual, moving droplet, introducing additional difficulty in theoretical treatment. Aslanov and Shamshev 557 presented an elementary mathematical model of this highly transient phenomenon, formulated on the basis of the theory of hydrodynamic instability on the droplet-gas interface. The model and approach may be used to make estimations of the range of droplet sizes and to calculate droplet breakup in high-speed flows behind shock waves, characteristic of detonation spray processes. 

The solution procedure to this equation is the same as described for the temporal isothermal species equations described above. In addition, the associated temperature sensitivity equation can be simply obtained by taking the derivative of Eq. (2.87) with respect to each of the input parameters to the model. The governing equations for similar types of homogeneous reaction systems can be developed for constant volume systems, and stirred and plug flow reactors as described in Chapters 3 and 4 and elsewhere [31-37], The solution to homogeneous systems described by Eq. (2.81) and Eq. (2.87) are often used to study reaction mechanisms in the absence of mass diffusion. These equations (or very similar ones) can approximate the chemical kinetics in flow reactor and shock tube experiments, which are frequently used for developing hydrocarbon combustion reaction mechanisms. 

The distribution of pressure, temperature, and density behind the shock depends upon the fraction of material reacted. If the reaction rate is exponentially accelerating (i.e., follows an Arrhenius law and has a relatively large overall activation energy like that normally associated with hydrocarbon oxidation), the fraction reacted changes very little initially the pressure, density, and temperature profiles are very flat for a distance behind the shock front and then change sharply as the reaction goes to completion at a high rate. 

---