Chemistry of the incomplete decomposition of ammonium perchlorate (AP)

Results are presented to show that as the thermal decomposition of orthorhombic ammonium perchlorate proceeds there is an accumulation, in the solid, of hydrochloric and nitric acids, the concentrations of which increase up to 15% decomposition after which they decrease until they reach the original values.

Combustion of ammonium perchlorate-based composite propellants in presence of methylammonium perchlorates

The effect of tri- and tetramethylammonium perchlorates (MAP-3 and MAP-4) on the burning rate of ammonium perchlorate (AP) based propellants has been determined at various pressures. Both additives increase the burning rate; however, MAP-3 has a moderate effect, whereas MAP-4 has a rather large effect. To explain the results, the thermal decomposition and calorimetric values of the propellants having these additives have been examined. Compound MAP-3 affects the thermal decomposition rate considerably, whereas MAP-4 has virtually no effect on the decomposition rate. The contrasting effects of MAP-4 on decomposition and burning rate suggest that the enhancement of burning rate may be due to the catalysis of gas-phase reactions. Further, detailed differences between behaviour of MAP-3, and MAP-4 appear to be attributable to the melting and low-temperature exotherm of MAP-3 and nonmelting and high-temperature exotherm of MAP-4.

Effect of electric field on ammonium perchlorate decomposition

A novel method of detecting the charge-carrying species in inorganic decomposable salts is described. In ammonium perchlorate it is observed that the charge-carrying species at temperatures 150 and 230°C are oppositely charged; i.e., they are negatively charged (ClO−4 ions) at 230°C and positively charged (H+ or NH+4) at 150°C.

The structure of ammonium oxalohydroxamate - a monopropellant

Abstract. NHn+.C2H3NzO4, Mr= 137.1, triclinic, Pi, a=3-952(1), b=6.772(1), c=9.993(1)A, a= 98.06 (1), fl= 89.96 (1), ~= 106.96 (1) °. V=253.06 A 3, z = 2, 2(Cu Ka) = 1.5418 A, g =15.29 cm -~, D m = 1.805, D x = 1.798 g cm -3, F(000)= 144, T= 293 K, R = 0.048 for 795 observed reflections. The unit cell contains two independent centrosymmetric molecules, one centred at (0,0,0) and the other at (0.5, 0.0, 0.5). The presence of experimentally determined~N-H groups and the -C=O bond lengths of 1.248 (4) and 1.247 (4)A indicate that the compound exists in the oxamic rather than the oximic form. Only one hydroxyl hydrogen is associated with each molecule. They are located at centres of inversion (0,0.5,0 and 0,0.5,0.5) and are shared between symmetry-related molecules via short symmetric H bonds with O...O=2.454(4), 2.457(4) and all O-H = 1.23 A

Effect of √-irradiation on the structure and dynamics of domains in triglycine selenate

A comparative study of the switching properties of pure and √-irradiated TGSe crystals has been carried out to see the effect of irradiation on the structure and dynamics of domains. The switching behaviour of √-irradiated TGSe has been found to be qualitatively similar to that of unirradiated crystal and this has been interpreted in terms of structural inhibition caused by the formation of radiolysis products as well as the difference between the domain structures of the unirradiated and irradiated samples. Confirmation of this has been obtained by studying the domain patterns using the etch method.

Effect of electric field on ammonium perchlorate decomposition

A novel method of detecting the charge-carrying species in inorganic decomposable salts is described. In ammonium perchlorate it is observed that the charge-carrying species at temperatures 150 and 230°C are oppositely charged; i.e., they are negatively charged (ClO−4 ions) at 230°C and positively charged (H+ or NH+4) at 150°C.

Chiral gels derived from secondary ammonium salts of (1R, 3S)-(+)-camphoric acid

In order to have access to chiral gels, a series of salts derived from (1R, 3S)-(+)-camphoric acid and various secondary amines were prepared based on supramolecular synthon rationale. Out of seven salts prepared, two showed moderate gelation abilities. The gels were characterized by differential scanning calorimetry, table top rheology, scanning electron microscopy, single crystal and powder X-ray diffraction. Structure property correlation based on X-ray diffraction techniques remain inconclusive indicating that some of the integrated part associated with the gelation phenomena requires a better understanding.

Thermal reactivity of ammonium perchlorate crystallised from solutions having different pH

The thermal reactivity of ammonium perchlorate was found to be dependent on the pH of the solution from which it had been crystallised. A nitric acid-crystallised sample reacted faster than an ammonium hydroxide-crystallised one.

Preparation and characterization of hydrazine derivatives. Part-II: Reaction of transition metal ammonium double sulphates with hydrazine hydrate

Transition metal ammonium double sulphates (NH4)2M(SO4)2· 6H2O, where M = Fe, Co and Ni react with hydrazine hydrate in air giving crystalline compounds of the general formula (N2H5) [M(N2H3COO)3] H2O. The reaction proceeds through (N2H5)2 M(SO4)2, · 3N2H4, (N2H5)2 [M(OH)4 · (N2H4)2], M(N2H3COO)2 · (N2H4)2 and N2H5 [M(N2 H3 COO)3] intermediates. The reaction sequence is followed by chemical analysis and infrared spectra. A possible reaction mechanism has been suggested.

A Convenient Methodology for the Selective Reduction of Carboxylic Acids With Benzyltriethyl-Ammonium Borohydride—Chlorotrimethylsilane

A combination of benzyltriethylammonium borohydride and chlorotrimethylsilane (1:1) in dichloromethane (0-25°C) has been found to be a convenient reagent system for the selective reduction of carboxylic acids to alcohols.

Novel kinetic scheme for the ammonium perchlorate gas phase

A novel gas-phase kinetic scheme for ammonium perchlorate (AP) deflagration involving 22 reactions among 18 species is developed. The kinetic scheme is based on a study of the effect of initial conditions on the solution of the differential equations of adiabatic constant-pressure combustion kinetics. The existence of condensed-phase reaction products providesalternate pathways for the consumption of NH3 and HCIOl produced by gas-phase dissociation of AP. Theoretically obtained temperature-time profiles of the novel scheme do not change when the conventional reaction pathways are included, indicatingthat the novel scheme is a substantially faster rate process. The new scheme does not involve the species CIO, which has long been considered a critical component of the AP gas phase and which is included in the conventional reaction pathways.The new scheme develops faster overall reaction rates, steeper temperature-time profiles, and in a deflagration model will result in higher heat-transfer rates from gas phase to the condensed phase.

A Thermodynamic Proposal for the Exposition of Critically and other Subtle Features in Self-Deflagrating Ammonium Perchlorate Systems

A first comprehensive investigation on the deflagration of ammonium perchlorate (AP) in the subcritical regime, below the low pressure deflagration limit (LPL, 2.03 MPa) christened as regime I$^{\prime}$, is discussed by using an elegant thermodynamic approach. In this regime, deflagration was effected by augmenting the initial temperature (T$_{0}$) of the AP strand and by adding fuels like aliphatic dicarboxylic acids or polymers like carboxy terminated polybutadiene (CTPB). From this thermodynamic model, considering the dependence of burning rate ($\dot{r}$) on pressure (P) and T$_{0}$, the true condensed (E$_{\text{s,c}}$) and gas phase (E$_{\text{s,g}}$) activation energies, just below and above the surface respectively, have been obtained and the data clearly distinguishes the deflagration mechanisms in regime I$^{\prime}$ and I (2.03-6.08 MPa). Substantial reduction in the E$_{\text{s,c}}$ of regime I$^{\prime}$, compared to that of regime I, is attributed to HClO$_{4}$ catalysed decomposition of AP. HClO$_{4}$ formation, which occurs only in regime I$^{\prime}$, promotes dent formation on the surface as revealed by the reflectance photomicrographs, in contrast to the smooth surface in regime I. The HClO$_{4}$ vapours, in regime I$^{\prime}$, also catalyse the gas phase reactions and thus bring down the E$_{\text{s,g}}$ too. The excess heat transferred on to the surface from the gas phase is used to melt AP and hence E$_{\text{s,c}}$, in regime I, corresponds to the melt AP decomposition. It is consistent with the similar variation observed for both the melt layer thickness and $\dot{r}$ as a function of P. Thermochemical calculations of the surface heat release support the thermodynamic model and reveal that the AP sublimation reduces the required critical exothermicity of 1108.8 kJ kg$^{-1}$ at the surface. It accounts for the AP not sustaining combustion in the subcritical regime I$^{\prime}$. Further support for the model comes from the temperature-time profiles of the combustion train of AP. The gas and condensed phase enthalpies, derived from the profile, give excellent agreement with those computed thermochemically. The $\sigma _{\text{p}}$ expressions derived from this model establish the mechanistic distinction of regime I$^{\prime}$ and I and thus lend support to the thermodynamic model. On comparing the deflagration of strand against powder AP, the proposed thermodynamic model correctly predicts that the total enthalpy of the condensed and gas phases remains unaltered. However, 16% of AP particles undergo buoyant lifting into the gas phase in the `free board region' (FBR) and this renders the demarcation of the true surface difficult. It is found that T$_{\text{s}}$ lies in the FBR and due to this, in regime I$^{\prime}$, the E$_{\text{s,c}}$ of powder AP matches with the E$_{\text{s,g}}$ of the pellet. The model was extended to AP/dicarboxylic acids and AP/CTPB mixture. The condensed ($\Delta $H$_{1}$) and gas phase ($\Delta $H$_{2}$) enthalpies were obtained from the temperature profile analyses which fit well with those computed thermochemically. The $\Delta $H$_{1}$ of the AP/succinic acid mixture was found just at the threshold of sustaining combustion. Indeed the lower homologue malonic acid, as predicted, does not sustain combustion. In vaporizable fuels like sebacic acid the E$_{\text{s,c}}$ in regime I$^{\prime}$, understandably, conforms to the AP decomposition. However, the E$_{\text{s,c}}$ in AP/CTPB system corresponds to the softening of the polymer which covers AP particles to promote extensive condensed phase reactions. The proposed thermodynamic model also satisfactorily explains certain unique features like intermittent, plateau and flameless combustion in AP/ polymeric fuel systems.