Luminous flame reaction

Assemble the apparatus shown in Fig. 1 V, 67, 1 this is self-explanatory. The distilling flask has a capacity of 250 ml. and the beaker contains 150 ml. of 10 per cent, sodium hydroxide solution. All corks must fit well and should be coated with paraflSn wax (by dipping into molten wax, and allowing to drain). Place half of the yield of the dry phenyldiazonium fluoborate in the distilling flask. Heat the solid gently with a small luminous flame at one point near its surface until decomposition begins withdraw the flame and allow the reaction to continue... 

Chemical Reactions. It burns with a luminous flame and is readily expld (Ref 2). It is reduced with Zn dust and Na hydroxide to dimethyl hydrazine (Ref 2). Action of coned HC1 forms methylhydrazine and formaldehyde (Ref 2). Treatment in anhyd eth with Na metal forms a solid adduct which gives dimethylhydrazine on addn of w (Ref 4). For a review of thermal and photochem reactions see Ref 8 Explosive Limits. In mixts with air the crit press at which exp] occurs varies inversely with temp betw 350 and 380° (Ref 6)... 

Recently revised test methods have revealed that nonluminous or barely luminous combustion reactions are occurring where previously it was reported that no combustion activity was occurring based on flame observance. 

If a stream of hydrogen issues into air and a light is applied to it, it burns (in accordance with the above equation) with an almost non-luminous flame (This reaction is, of course, reversible, i.e. a stream of air would burn in the same way in an atmosphere of hydrogen.) It was discovered by Frankland that while at atmospheric pressure the flame of hydrogen burning in oxygen is almost non-luminous if the pressure is... 

The combustion wave of HMX is divided into three zones crystallized solid phase (zone 1), solid and/or liquid condensed phase (zone 11), and gas phase (zone 111). A schematic representation of the heat transfer process in the combustion wave is shown in Fig. 5.5. In zone 1, the temperature increases from the initial value Tq to the decomposition temperature T without reaction. In zone 11, the temperature increases from T to the burning surface temperature Tj (interface of the condensed phase and the gas phase). In zone 111, the temperature increases rapidly from to the luminous flame temperature (that of the flame sheet shown in Fig. 5.4). Since the condensed-phase reaction zone is very thin (-0.1 mm), is approximately equal to T . 

The soUd-phase reaction zone is also termed the subsurface reaction zone or condensed-phase reaction zone . As the dark zone reaction represents an induction zone ahead of the flame zone, the dark zone is also termed the preparation zone when it produces a luminous flame. Since the flame zone is luminous, it is also termed the luminous flame zone . 

The third chemical equation, involving nitric oxide, represents a termolecular reaction. Therefore, the overall order of the reaction is expected to exceed that of the second-order reaction generally assumed in the pre-mixed gas burning model. The high exothermicity accompanying the reduction of NO to N2 is responsible for the appearance of the luminous flame in the combustion of a double-base propellant, and hence the flame disappears when insufScient heat is produced in this way, i. e., during fizz burning. 

In the dark zone, the temperature increases relatively slowly and so for the most part the temperature gradient is much less steep than that in the fizz zone. However, the temperature increases rapidly at about 50 pm from where the flame reaction starts to produce the luminous flame zone. The gas flow velocity increases with increasing distance due to the increase in temperature. The mole fractions of NO, CO, and Hj decrease and those of N2, CO2, and H2O increase with increasing distance in the dark zone. The results imply that the overall reaction in the dark zone is highly exothermic and that the order of reaction is higher than second order because of the reduction reaction involving NO. The derivative of temperature with respect to time t in the dark zone is expressed empirically by the formulal =l... 

Since the final gas-phase reaction to produce a luminous flame zone is initiated by the reaction in the dark zone, the reaction time is determined by the dark zone length, L4, i. e., the flame stand-off distance. Fig. 6.8 and 6.9 show data for the dark zone length and the dark zone temperature, T, respectively, for the propellants listed in Table 6.3. The luminous flame front approaches the burning surface and... 

The reaction time to produce the luminous flame, is given by... 

The combustion wave of an NC-NG-GAP propellant consists of successive two-stage reaction zones.0 1 The first gas-phase reaction occurs at the burning surface and the temperature increases rapidly in the fizz zone. The second zone is the dark zone, which separates the luminous flame zone from the burning surface. Thus, the luminous flame stands some distance above the burning surface. This structure... 

Most importantly, the presence of lead compounds results in a strong acceleration of the fizz zone reactions, i. e., those in the gas phase close to the burning surface. Acceleration of the reactions in the subsequent dark zone or in the luminous flame zone is not significant. The net result of the fizz zone reaction rate acceleration is an increased heat feedback to the surface (e. g., by as much as 100 %), which produces super-rate burning. 

The dark zone length of liF-catalyzed propellants is increased by the addition of LiF in the region of super-rate burning, similar to the case of Pb-catalyzed propellants, as shown in Fig. 6.28. Table 6-11 shows the dark zone lengths and reaction times Xg in the dark zone producing the luminous flame at two different pressures,... 

However, the luminous flame front rapidly approaches the burning surface when the pressure is increased. This reaction is also caused by the reduction of NO to N2, as in the reaction process of double-base propellants. 

Fig. 7.45 shows a set of flame photographs of HMX-GAP propellants with and without catalysts. The luminous flame front of the non-catalyzed propellant is almost attached the burning surface at 0.5 MPa (a). When the propellant is catalyzed, the luminous flame is distended from the burning surface at the same pressure (b). Since the heat flux transferred back from the gas phase and the heat of reaction at... 

The combustion wave of an HMX composite propellant consists of successive re-achon zones the condensed-phase reachon zone, a first-stage reaction zone, a second-stage reaction zone, and the luminous flame zone. The combustion wave structure and temperature distribution for an HMX propellant are shown in Fig. 7.47. In the condensed-phase reaction zone, HMX particles melt together with the polymeric binder HTPE and form an energetic liquid mixture that covers the burning surface of the propellant. In the first-stage reaction zone, a rapid exother-... 

When large spherical AP particles dg = 3 mm) are added, large flamelets are formed in the dark zone.Pl Close inspection of the AP particles at the burning surface reveals that a transparent bluish flame of low luminosity is formed above each AP particle. These are ammonia/perchloric acid flames, the products of which are oxidizer-rich, as are also observed for AP composite propellants at low pressures, as shown in Fig. 7.5. The bluish flame is generated a short distance from the AP particle and has a temperature of up to 1300 K. Surrounding the bluish flame, a yellowish luminous flame stream is formed. This yellowish flame is produced by in-terdiffusion of the gaseous decomposition products of the AP and the double-base matrix. Since the decomposition gas of the base matrix is fuel-rich and the temperature in the dark zone is about 1500 K, the interdiffusion of the products of the AP and the matrix shifts the relative amounts towards the stoichiometric ratio, resulting in increased reaction rate and flame temperature. The flame structure of an AP-CMDB propellant is illustrated in Fig. 8.1. 

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