Decomposition of ammonium

The thermal decomposition of ammonium succinate gives a good yield of succlnimlde ... 

Table 17. Thermochemical Data for the Decomposition of Ammonium Nitrate...

High Purity Aluminum Trifluoride. High purity anhydrous aluminum triduoride that is free from oxide impurities can be prepared by reaction of gaseous anhydrous HF and AlCl at 100°C, gradually raising the temperature to 400°C. It can also be prepared by the action of elemental fluorine on metal/metal oxide and subsequent sublimation (12) or the decomposition of ammonium duoroaluminate at 700°C. 

Hafnium Halides. Hafnium tetrafluoride, HfF, can be prepared by careful thermal decomposition of ammonium fluorohafnate in an... 

A number of manufacturers around the world are using the decomposition of ammonium dichromate to produce chrome oxide (eq. 5) (78). Generally, an excess of finely ground ammonium sulfate is mixed with sodium dichromate, and the dry mixture is heated to form chrome oxide and sodium sulfate, evolving nitrogen and steam. 

The decomposition of ammonium nitrate, an explosive, evolves 37.0 kj/mol. Use the reaction given in Problem 45 to calculate the mass of ammonium nitrate (in kilograms) required to produce the same amount of energy as that produced when one milligram of U-235 undergoes fission. 

Other methods exist for the precipitation of tantalum and niobium hydroxides for subsequent use as oxide precursors. Application of ammonium carbonate, (NH4)2C03, instead of ammonia solution, also seems to have potential for the precipitation of tantalum and niobium hydroxides. Ammonium carbonate is relatively stable in aqueous media at room temperature and does not initiate the precipitation of hydroxides. Increasing the temperature of the solution causes hydrolysis and decomposition of ammonium carbonate yielding hydroxyl ions and an increase in pH, as follows ... 

Subsequent steps of the process involve the decomposition of ammonium peroxometalates, (NH4)3Ta08 and (NH4)3Ta08, which takes place according to a hydrolytic mechanism. Belov et al. [512] presents the following interactions as occurring by different mechanisms in different media. Hydrolysis in acidic media at pH < 3 appears to occur with the separation of oxygen, as shown in Equation (152) ... 

Factors which Catalyze the Decomposition of Ammonium Perchlorate. Irradiation of AP with X-rays or gamma radiation causes it to decomp at a lower temp, presumably by the formn of holes or active sites in the cryst (Ref 36). Metal salts have been found to lower the decompn point of AP by as much as 80° (Ref 39), and to lower the induction period for its expln at 233° by 21 minutes (Ref 41). Inorg salts which have been found to catalyze the decompn of AP are listed below ... 

Adiabatic Decomposition of Ammonium Perchlorate , SRI Report PU-3573 (1965), AD 640084 33) M.L. Essick, Literature Search. ... 

The Thermal Decomposition of Ammonium Perchlorate — A Literature Review , U of Miami. Dept of Chem Special Report 6 (1968), AD 673542 43) O, Svejka, CzechP 129074... 

Heath and Majer (H3) have recently used a mass spectrometer to study the decomposition of ammonium perchlorate. Decomposition was detected in the range from 110° to 120°C. At this temperature, there were ions in the mass spectrum caused by NH3, HC104, Cl2, HC1, nitrogen oxides, and 02. The appearance of the species NO, N02,02, and Cl2 in the decomposition products under very low pressure (i.e., in the absence of gas-phase molecular collisions) indicates that the principal decomposition reactions take place in the crystal and not in the gas phase. 

Catalysts which enhance the burning rate of composite propellants are generally believed to accelerate the decomposition of ammonium perchlorate, but the catalytic mechanism is still not very clear. The important observed aspects of this catalysis can be summarized as follows ... 

Horton (H9, H10) has obtained additional acoustic-admittance data for a series of composite propellants. At a given frequency, decreasing the mean oxidizer particle size increases the acoustic admittance and thereby the tendency for instability. Horton also investigated the effects on the acoustic admittance of the incorporation of traces of copper chromite, a known catalyst, for the decomposition of ammonium perchlorate, lithium fluoride (a burning-rate depressant), and changes in binder these data are difficult to analyze because of experimental errors. 

Accumulatory pressure measurements have been used to study the kinetics of more complicated reactions. In the low temperature decomposition of ammonium perchlorate, the rate measurements depend on the constancy of composition of the non-condensable components of the product mixture [120], The kinetics of the high temperature decomposition [ 59] of this compound have been studied by accumulatory pressure measurements in the presence of an inert gas to suppress sublimation of the solid reactant. Reversible dissociations are not, however, appropriately studied in a closed system, where product readsorption and diffusion effects within the product layer may control, or exert perceptible influence on, the rate of gas release [121]. 

Methods of EGA using selective sorption, condensation of effluent gases, infrared absorption and thermoparticulate analysis have been reviewed by Lodding [144]. The use of simple gas burette systems should not be forgotten and an Orsat gas analysis apparatus can provide useful measurements in studies of the decomposition of formates [169]. Problems have been encountered in the determination of water released Kiss et al. [170—172] have measured the formation of this compound from infrared analyses of the acetylene evolved following reaction of water with calcium carbide. Kinetic data may be obtained by wet methods ammonia, determined by titration after absorption in an aqueous solution, has been used to measure a—time values for the decomposition of ammonium salts in a fluidized bed [173],... 

Some limitations of optical microscopy were apparent in applying [247—249] the technique to supplement kinetic investigations of the low temperature decomposition of ammonium perchlorate (AP), a particularly extensively studied solid phase rate process [59]. The porous residue is opaque. Scanning electron microscopy showed that decomposition was initiated at active sites scattered across surfaces and reaction resulted in the formation of square holes on m-faces and rhombic holes on c-faces. These sites of nucleation were identified [211] as points of intersection of line dislocations with an external boundary face and the kinetic implications of the observed mode of nucleation and growth have been discussed [211]. 

Although it would appear that plots of ln[—ln(l — a)] against ln(f — t0) provide the most direct method for the determination of n from experimental a—time data, in practice this approach is notoriously insensitive and errors in t0 exert an important control over the apparent magnitude of n. An alternative possibility is to compare linearity of plots of [—ln(l — a)]1/n against t this has been successful in the kinetic analysis of the decomposition of ammonium perchlorate [268]. Another possibility is through the use of the differential form of eqn. (6)... 

The Avrami—Erofe ev equation, eqn. (6), has been successfully used in kinetic analyses of many solid phase decomposition reactions examples are given in Chaps. 4 and 5. For no substance, however, has this expression been more comprehensively applied than in the decomposition of ammonium perchlorate. The value of n for the low temperature reaction of large crystals [268] is reduced at a 0.2 from 4 to 3, corresponding to the completion of nucleation. More recently, the same rate process has been the subject of a particularly detailed and rigorous re-analysis by Jacobs and Ng [452] who used a computer to optimize curve fitting. The main reaction (0.01 < a < 1.0) was well described by the exact Avrami equation, eqn. (4), and kinetic interpretation also included an examination of the rates of development and of multiplication of nuclei during the induction period (a < 0.01). The complete kinetic expressions required to describe quantitatively the overall reaction required a total of ten parameters. 

Fig. 4. Reduced time plots, fr = (f/fo.s), for the isothermal decomposition of ammonium vanadyl oxalate using master data for the Avrami—Erofe ev equation [eqn. (6), n = 2], by the application of a method of analysis [73] described in the text. The circles are experimental measurements and the lines correspond to exact agreement with the equation. (Reproduced, with permission, from Thermochimica Acta.)...

Fig. 16. Graphical representation of Arrhenius parameters for the low temperature decomposition of ammonium perchlorate (pelleted, orthorhombic, o, and cubic, , forms). Compensation behaviour is observed. Data from Jacobs and Ng [452]. N = nucleation, B = branching, G = growth processes.

Fig. 17. Unified reaction scheme for the thermal decomposition of ammonium perchlorate, proposed by Jacobs et al. [59,925,926], In the low temperature reaction, the interaction occurs between adsorbed species (a) whereas the high temperature reaction and sublimation process involved volatilization intermediates (g). X] and X2 represent mixtures of intermediates.

NH4)2S03 sublimes unaltered [946] but the monohydrate undergoes partial decomposition to H20, NH3 and (NH4)2S207. Decomposition of ammonium thiosulphate is inhibited by the addition of other ammonium salts, e.g. (NH4)2C03, and by briquetting [947]. 

In general, ammonia is evolved before anion breakdown in the decompositions of ammonium metal nitrates [960,961], Decomposition of hydrazonium nitrate [962] obeys second-order kinetics and presumably occurs in a melt. 

Many of these salts melt or sublime before or during decomposition and reaction temperatures generally increase with molar mass. Thermal analyses for a selection of ammonium carboxylates have been given by Erdey et al. [915] who conclude that the base strength of the anion increases with temperature until it reaches that of NH3. Decompositions of ammonium acetate (>333 K) and ammonium oxalate (>473 K) proceed through amide formation. Ammonium benzoate and ammonium salicylate sublime (>373 K) without decomposition but ammonium citrate decomposes (>423 K) to yield some residual carbon. 

The first step in the decomposition of ammonium chromate is conversion to the dichromate [981] ( 375 K), the rate of this process being reduced by oxygen [982] (1—100 Torr). Thermoanalytical measurements have identified four stages in the decomposition [983], At 508 K... 

Reference has already been made to the dehydration of alums (Sect. 1.2 and Table 10), decomposition of ammonium metal phosphates (Sect. 4.1.5) and the use of KMn04—KCIO4 solid solutions in mechanistic studies of the decomposition of potassium permanganate (Sect. 3.6). 

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