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.

A thermodynamic protocol for explaining subcriticality and other subtle features in self-deflagrating solids

A novel universal approach to understand the self-deflagration in solids has been attempted by using basic thermodynamic equation of partial differentiation, where burning mte depends on the initial temperature and pressure of the system. Self-deflagrating solids are rare and are reported only in few compounds like ammonium perchlorate (AP), polystyrene peroxide and tetrazole. This approach has led us to understand the unique characteristics of AP, viz. the existence of low pressure deflagration limit (LPL 20 atm), hitherto not understood sufficiently. This analysis infers that the overall surface activation energy comprises of two components governed by the condensed phase and gas phase processes. The most attractive feature of the model is the identification of a new subcritical regime I' below LPL where AP does not burn. The model is aptly supported by the thermochemical computations and temperature-profile analyses of the combustion train. The thermodynamic model is further corroborated from the kinetic analysis of the high pressure (1-30 atm) DTA thermograms which affords distinct empirical decomposition rate laws in regimes I' and 1 (20-60 atm). Using Fourier-Kirchoff one dimensional heat transfer differential equation, the phase transition thickness and the melt-layer thickness have been computed which conform to the experimental data.

Behavior of Ca(OH)2/CaO pellet under dehydration and hydration

With construction of a thermochemical energy conversion prototype system to store solar heat, thermal dissociation of pellets of Ca(OH)2 and hydration of CaO have been investigated in some detail for its application to the system. The inorganic substance is very attractive as a material for long term heat storage, but molar density changes associated with the reaction are fairly large. Therefore, this factor has been taken into account in the kinetic equation. The importance of additives and pellet size has been discussed considering reactivity and strength of pellets. An analysis has been attempted when chemical reaction is important. The deformation of pellets was observed during hydration.

Solid state structural and solution studies on the formation of a flexible cavity for anions by copper(I) and 1,2-bis(diphenylphosphino)ethane

Copper(l) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu-2(dppe)(3)(X)(2) [X- = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu-2(dPPe)(3)](2+) dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1 -3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior. (C) 2002 Elsevier Science Ltd. All rights reserved.

Thermal degradation studies of para-substituted poly(styrene peroxide)s

The thermal degradation of a series of para-substituted poly(styrene peroxide)s with electron-donating [CH3, C(CH3)(3)] and electron-attracting (Br) substitutents are investigated by thermogravimetric analysis (TGA). The results indicate that the Hammett relationship can describe quantitatively the trends in maximum rate of polymer decomposition (T-max) observed in TGA and thus thermostability of substituted poly(styrene peroxide)s depends only on the electronic nature of substituents and their ability to stabilize macroradicals formed during chain scission. The experimental results are also substantiated by thermochemical calculations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Electrochemical measurement of the oxygen potential of the system iron+alumina+ hercynite in the temperature range 750 to 1600oC

Solid oxide galvanic cells using CaO-ZrO2 and CaO-ZrO2 in combination with YO1.5-ThO2 as electrolyte were used to determine the free energy of formation of hercynite from 750–1600°C. The formation reaction is 2Fe(s,1) + O2(g) + Al2O3(α) = 2FeO.Al2O3(s)for which ΔG° = − 139,790 + 32.83T (±300) cals. (750–1536°C) ΔG° = − 146,390 + 36.48T (±300) cals. (1536–1700°C)These measurements can be used to resolve the discrepancies that exist in published thermochemical data, and provide an accurate oxygen potential standard for calibrating and assessing the performance of oxygen probes under steelmaking conditions.

Corrosion of 310 stainless steel in H2 H2O-H2S gas mixtures; studies at constant temperature and fixed oxygen potential

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10-13 Nm-2 and sulfur potentials ranging from 0.19 × 10-2 Nm-2 to 33 × 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (P S 2 ± 2.7 × 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials (P S 2 ± 0.19 × 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

Experimental and computational studies on a gasifier based stove

The work reported here is concerned with a detailed thermochemical evaluation of the flaming mode behaviour of a gasifier based stove. Determination of the gas composition over the fuel bed, surface and gas temperatures in the gasification process constitute principal experimental features. A simple atomic balance for the gasification reaction combined with the gas composition from the experiments is used to determine the CH(4) equivalent of higher hydrocarbons and the gasification efficiency (eta g). The components of utilization efficiency, namely, gasification-combustion and heat transfer are explored. Reactive flow computational studies using the measured gas composition over the fuel bed are used to simulate the thermochemical flow field and heat transfer to the vessel; hither-to-ignored vessel size effects in the extraction of heat from the stove are established clearly. The overall flaming mode efficiency of the stove is 50-54%; the convective and radiative components of heat transfer are established to be 45-47 and 5-7% respectively. The efficiency estimates from reacting computational fluid dynamics (RCFD) compare well with experiments. (C) 2011 Elsevier Ltd. All rights reserved.

Tar characterisation in new generation agro-residue gasifiers - Cyclone and downdraft open top twin air entry systems

This paper deals with the characterisation of tar from two configurations of bioresidue thermochemical conversion reactors designed for producer gas based power generation systems. The pulverised fuel reactor is a cyclone system (R1) and the solid bioresidue reactor (denoted R2) is an open top twin air entry system both at 75-90 kg/h capacity (to generate electricity similar to 100 kVA). The reactor, R2, has undergone rigorous test in a major Indo-Swiss programme for the tar quantity at various conditions. The former is a recent technology development. Tars collected from these systems by a standard tar collection apparatus at the laboratory at Indian Institute of Science have been analysed at the Royal Institute of Technology (KTH), Sweden. The results of these analyses show that these thermochemical conversion reactors behave differently from the earlier reactors reported in literature in so far as tar generation is concerned. The extent of tar in hot gas is about 700-800 ppm for R1 and 70-100 ppm for R2. The amounts of the major compounds - naphthalene and phenol-are much lower that what is generally understood to happen in the gasifiers in Europe. It is suggested that the longer residence times at high temperatures allowed for in these reactors is responsible for this behavior. It is concluded the new generation reactor concepts extensively tried out at lower power levels hold promise for high power atmospheric gasification systems for woody as well as pulverisable bioresidues.

Oxy-steam gasification of biomass for hydrogen rich syngas production using downdraft reactor configuration

The paper focuses on the use of oxygen and steam as the gasification agents in the thermochemical conversion of biomass to produce hydrogen rich syngas, using a downdraft reactor configuration. Performance of the reactor is evaluated for different equivalence ratios (ER), steam to biomass ratios (SBR) and moisture content in the fuel. The results are compared and evaluated with chemical equilibrium analysis and reaction kinetics along with the results available in the literature. Parametric study suggests that, with increase in SBR, hydrogen fraction in the syngas increases but necessitates an increase in the ER to maintain reactor temperature toward stable operating conditions. SBR is varied from 0.75 to 2.7 and ER from 0.18 to 0.3. The peak hydrogen yield is found to be 104g/kg of biomass at SBR of 2.7. Further, significant enhancement in H-2 yield and H-2 to CO ratio is observed at higher SBR (SBR=1.5-2.7) compared with lower range SBR (SBR=0.75-1.5). Experiments were conducted using wet wood chips to induce moisture into the reacting system and compare the performance with dry wood with steam. The results clearly indicate the both hydrogen generation and the gasification efficiency ((g)) are better in the latter case. With the increase in SBR, gasification efficiency ((g)) and lower heating value (LHV) tend to reduce. Gasification efficiency of 85.8% is reported with LHV of 8.9MJNm(-3) at SBR of 0.75 compared with 69.5% efficiency at SBR of 2.5 and lower LHV of 7.4 at MJNm(-3) at SBR of 2.7. These are argued on the basis of the energy required for steam generation and the extent of steam consumption during the reaction, which translates subsequently in the LHV of syngas. From the analysis of the results, it is evident that reaction kinetics plays a crucial role in the conversion process. The study also presents the importance of reaction kinetics, which controls the overall performance related to efficiency, H-2 yield, H-2 to CO fraction and LHV of syngas, and their dependence on the process parameters SBR and ER. Copyright (c) 2013 John Wiley & Sons, Ltd.

Some Thermodynamic Aspects of the Oxides of Chromium

To understand Cr emissions from slag melts to a vapor phase, an assessment of the stabilities of the chromium oxides at high temperatures has been carried out. The objective of the present study is to present a set of consistent data corresponding to the thermodynamic properties of the oxides of chromium, with special reference to the emission of hexavalent chromium from slags. In the current work, critical analysis of the experimental data available and a third analysis in the case of Cr2O3 have been carried out. Commercial databases, Fact Sage and ThermoCalc along with NIST-JANAF Thermochemical Tables, have been used for the analysis and comparisons of the results that are presented. The significant discrepancies in the available data have been pointed out. The data from NIST-JANAF Thermochemical Tables have been found to provide a set of consistent data for the various chromium oxides. An Ellingham diagram and the equations for the Delta G degrees (standard Gibbs free energy change) of formation of CrOx have been proposed. The present analysis shows that CrO3(g) is likely to be emitted from slag melts at high oxygen partial pressures. (C) The Minerals, Metals & Materials Society and ASM International 2014

First and second law thermodynamic analysis of air and oxy-steam biomass gasification

Gasification is an energy transformation process in which solid fuel undergoes thermochemical conversion to produce gaseous fuel, and the two most important criteria involved in such process to evaluate the performance, economics and sustainability of the technology are: the total available energy (exergy) and the energy conserved (energy efficiency). Current study focuses on the energy and exergy analysis of the oxy-steam gasification and comparing with air gasification to optimize the H-2 yield, efficiency and syngas energy density. Casuarina wood is used as a fuel, and mixture of oxygen and steam in different proportion and amount is used as a gasifying media. The results are analysed with respect to varying equivalence ratio and steam to biomass ratio (SBR). Elemental mass balance technique is employed to ensure the validity of results. First and second law thermodynamic analysis is used towards time evaluation of energy and exergy analysis. Different component of energy input and output has been studied carefully to understand the influence of varying SBR on the availability of energy and irreversibility in the system to minimize the losses with change in input parameters for optimum performance. The energy and exergy losses (irreversibility) for oxy-steam gasification system are compared with the results of air gasification, and losses are found to be lower in oxy-steam thermal conversion; which has been argued and reasoned due to the presence of N-2 in the air-gasification. The maximum exergy efficiency of 85% with energy efficiency of 82% is achieved at SBR of 0.75 on the molar basis. It has been observed that increase in SBR results in lower exergy and energy efficiency, and it is argued to be due to the high energy input in steam generation and subsequent losses in the form of physical exergy of steam in the product gas, which alone accounts for over 18% in exergy input and 8.5% in exergy of product gas at SBR of 2.7. Carbon boundary point (CBP), is identified at the SBR of 1.5, and water gas shift (WGS) reaction plays a crucial role in H-2 enrichment after carbon boundary point (CBP) is reached. Effects of SBR and CBP on the H-2/CO ratio is analysed and discussed from the perspective of energy as well as the reaction chemistry. Energy density of syngas and energy efficiency is favoured at lower SBR but higher SBR favours H-2 rich gas at the expense of efficiency. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Boundary-layer transition on a slender cone in hypervelocity flow with real gas effects

The laminar to turbulent transition process in boundary layer flows in thermochemical nonequilibrium at high enthalpy is measured and characterized. Experiments are performed in the T5 Hypervelocity Reflected Shock Tunnel at Caltech, using a 1 m length 5-degree half angle axisymmetric cone instrumented with 80 fast-response annular thermocouples, complemented by boundary layer stability computations using the STABL software suite. A new mixing tank is added to the shock tube fill apparatus for premixed freestream gas experiments, and a new cleaning procedure results in more consistent transition measurements. Transition location is nondimensionalized using a scaling with the boundary layer thickness, which is correlated with the acoustic properties of the boundary layer, and compared with parabolized stability equation (PSE) analysis. In these nondimensionalized terms, transition delay with increasing CO₂ concentration is observed: tests in 100% and 50% CO₂, by mass, transition up to 25% and 15% later, respectively, than air experiments. These results are consistent with previous work indicating that CO₂ molecules at elevated temperatures absorb acoustic instabilities in the MHz range, which is the expected frequency of the Mack second-mode instability at these conditions, and also consistent with predictions from PSE analysis. A strong unit Reynolds number effect is observed, which is believed to arise from tunnel noise. N_Tr for air from 5.4 to 13.2 is computed, substantially higher than previously reported for noisy facilities. Time- and spatially-resolved heat transfer traces are used to track the propagation of turbulent spots, and convection rates at 90%, 76%, and 63% of the boundary layer edge velocity, respectively, are observed for the leading edge, centroid, and trailing edge of the spots. A model constructed with these spot propagation parameters is used to infer spot generation rates from measured transition onset to completion distance. Finally, a novel method to control transition location with boundary layer gas injection is investigated. An appropriate porous-metal injector section for the cone is designed and fabricated, and the efficacy of injected CO₂ for delaying transition is gauged at various mass flow rates, and compared with both no injection and chemically inert argon injection cases. While CO₂ injection seems to delay transition, and argon injection seems to promote it, the experimental results are inconclusive and matching computations do not predict a reduction in N factor from any CO₂ injection condition computed.

Oxy anion-accelerated rearrangements

The alkali metal salts of 1,5-hexadien-3-ols undergo accelerated Cope rearrangements to the enolates of δ, ε-unsaturated carbonyl compounds. The generality of the rearrangement was investigated in numerous systems, particularly acyclic cases, and the effect of changes in substituents, counterions, solvents, and geometrical structures were noted and discussed. Applications of this methodology in synthesis included the synthesis of the insect pheromone frontalin, the preparation of selectively monoprotected 1,6-dicarbonyl compounds from 4-methoxy- and 4-phenylthio-1,5-hexadien-3-ols, and the construction of complex ring structures such as a D-homo-estratetraenone derivative.

Thermochemical estimates of the energetics of anionpromoted alkoxide fragmentations were made, and in all cases heterolytic cleavage was favored over hemolytic cleavage by 8.5-53 kcal/mol. The implication of these and other thermochemical estimates is that the anionic oxy-Cope rearrangement occurs via a concerted mechanism rather than a dissociation-recombination process. The concepts of anion-induced bond weakening were successfully applied to an accelerated [1,3]-shift of a dithiane fragment in a cyclohexenyl system. Trapping experiments demonstrated that > 85% of the [1,3]-shift occurred within a solvent cage. Attempts at promoting an intramolecular ene reaction using the potassium salts of 2,7-octadien-1-o1 and 2,8-nonadien-1-o1 were unsuccessful. A general review of anion-promoted bond reorganizations and anion substituent effects is also presented.