The thermal decomposition of ammonium perchlorate at low temperatures

The thermal decomposition of ammonium perchlorate shows several unusual characteristics. The most striking of these is that at low temperatures it decomposes only to the extent of about 20 to 30 %, leaving a residue which is chemically identical with the original salt. The experimental results for the rate of decomposition of whole crystals, powder and pellets are shown to be well fitted by a kinetic equation which is in accord with a detailed model for the decomposing salt. It is possible to account in terms of this model (which involves the decomposition of intergranular material only) for the observed dependence of the activation energy on the extent of cold-working to which the solid is subjected.

1947 ◽  
Vol 25b (2) ◽  
pp. 135-150 ◽  
Author(s):  
Paul A. Giguère

The decomposition of hydrogen peroxide vapour has been investigated at low pressures (5 to 6 mm.) in the temperature range 50° to 420 °C., for the purpose of determining the effect of the nature and treatment of the active surfaces. The reaction was followed in an all-glass apparatus and, except in one case, with one-litre round flasks as reaction vessels. Soft glass, Pyrex, quartz, and metallized surfaces variously treated were used. In most cases the decomposition was found to be mainly of the first order but the rates varied markedly from one vessel to another, even with vessels made of the same type of glass. On a quartz surface the decomposition was preceded by an induction period at low temperatures. Fusing the glass vessels slowed the reaction considerably and increased its apparent activation energy; this effect was destroyed by acid washing. Attempts to poison the surface with hydrocyanic acid gave no noticeable result. The marked importance of surface effects at all temperatures is considered as an indication that the reaction was predominantly heterogeneous under the prevailing conditions. Values ranging from 8 to 20 kcal. were found for the apparent energy of activation. It is concluded that the decomposition of hydrogen peroxide vapour is not very specific as far as the nature of the catalyst is concerned.


1972 ◽  
Vol 50 (7) ◽  
pp. 992-998 ◽  
Author(s):  
C. J. Chen ◽  
D. J. McKenney

Kinetics of the thermal decomposition of pure formaldehyde were studied over a temperature range of 466–516 °C and a pressure range of ~ 50–160 Torr. Arrhenius parameters and rate laws were determined for carbon monoxide, hydrogen and methanol as follows:[Formula: see text]A mechanism is postulated which is qualitatively consistent with the experimental results but the activation energy for reaction 1[Formula: see text]is ~15 kcal/mol lower than predicted from recent thermochemical data, suggesting the possibility of a heterogeneous reaction.


1994 ◽  
Vol 59 (10) ◽  
pp. 2253-2261 ◽  
Author(s):  
Samih A. Halawy ◽  
Mohamed A. Mohamed

The effect of addition of MoO3 and Fe2O3 as well as mixtures of the two oxides (calcined in air at 500 °C) on the thermal decomposition of ammonium perchlorate (AP) was studied using thermogravimetry (TGA) and derivative thermogravimetric analysis (DTG). The catalysts calcined at 500 °C were characterized using TPR, XPS and XRD techniques. The surface area of the catalysts was determined by means of the conventional BET method. The results are discussed in terms of the recently published mechanism in which nitryl perchlorate is supposed as an intermediate in the thermal decomposition of pure AP. The correlation between the surface area and activity of the catalysts in the thermal decomposition of AP has been done. The activation energy (∆E) for non-catalyzed and catalyzed high-temperature thermal decomposition of AP were calculated from the TGA results using the Coats-Redfern equation.


2021 ◽  
Vol 35 (5) ◽  
pp. 4447-4456
Author(s):  
Xiaoge Han ◽  
Linyu Zhou ◽  
Shaobo Cao ◽  
Liangliang Zhang ◽  
Guolei Xiang ◽  
...  

Energies ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1316
Author(s):  
Daniel Mahon ◽  
Gianfranco Claudio ◽  
Philip Eames

To improve the energy efficiency of an industrial process thermochemical energy storage (TCES) can be used to store excess or typically wasted thermal energy for utilisation later. Magnesium carbonate (MgCO3) has a turning temperature of 396 °C, a theoretical potential to store 1387 J/g and is low cost (~GBP 400/1000 kg). Research studies that assess MgCO3 for use as a medium temperature TCES material are lacking, and, given its theoretical potential, research to address this is required. Decomposition (charging) tests and carbonation (discharging) tests at a range of different temperatures and pressures, with selected different gases used during the decomposition tests, were conducted to gain a better understanding of the real potential of MgCO3 for medium temperature TCES. The thermal decomposition (charging) of MgCO3 has been investigated using thermal analysis techniques including simultaneous thermogravimetric analysis and differential scanning calorimetry (TGA/DSC), TGA with attached residual gas analyser (RGA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (up to 650 °C). TGA, DSC and RGA data have been used to quantify the thermal decomposition enthalpy from each MgCO3.xH2O thermal decomposition step and separate the enthalpy from CO2 decomposition and H2O decomposition. Thermal analysis experiments were conducted at different temperatures and pressures (up to 40 bar) in a CO2 atmosphere to investigate the carbonation (discharging) and reversibility of the decarbonation–carbonation reactions for MgCO3. Experimental results have shown that MgCO3.xH2O has a three-step thermal decomposition, with a total decomposition enthalpy of ~1050 J/g under a nitrogen atmosphere. After normalisation the decomposition enthalpy due to CO2 loss equates to 1030–1054 J/g. A CO2 atmosphere is shown to change the thermal decomposition (charging) of MgCO3.xH2O, requiring a higher final temperature of ~630 °C to complete the decarbonation. The charging input power of MgCO3.xH2O was shown to vary from 4 to 8136 W/kg with different isothermal temperatures. The carbonation (discharging) of MgO was found to be problematic at pressures up to 40 bar in a pure CO2 atmosphere. The experimental results presented show MgCO3 has some characteristics that make it a candidate for thermochemical energy storage (high energy storage potential) and other characteristics that are problematic for its use (slow discharge) under the experimental test conditions. This study provides a comprehensive foundation for future research assessing the feasibility of using MgCO3 as a medium temperature TCES material. Future research to determine conditions that improve the carbonation (discharging) process of MgO is required.


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