Thermal decomposition of rare-earth trioxalatocobaltates

The thermal decomposition of rare-earth trioxalatocobaltates LnCo(C2O4)3 · x H2O, where Ln = La, Pr, Nd, has been studied in flowing atmospheres of air/oxygen, argon/ nitrogen, carbon dioxide and a vacuum. The compounds decompose through three major steps, viz. dehydration, decomposition of the oxalate to an intermediate carbonate, which further decomposes to yield rare-earth cobaltite as the final product. The formation of the final product is influenced by the surrounding gas atmosphere. Studies on the thermal decomposition of photodecomposed lanthanum trioxalatocobaltate and a mechanical mixture of lanthanum oxalate and cobalt oxalate in 1 : 2 molar ratio reveal that the decomposition behaviour of the two samples is different. The drawbacks of the decomposition scheme proposed earlier have been pointed out, and logical schemes based on results obtained by TG, DTA, DTG, supplemented by various physico-chemical techniques such as gas and chemical analyses, IR and mass spectroscopy, surface area and magnetic susceptibility measurements and X-ray powder diffraction methods, have been proposed for the decomposition in air of rare-earth trioxalatocobaltates as well as for the photoreduced lanthanum salt and a mechanical mixture of lanthanum and cobalt oxalates.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.

Thermal decomposition of sulphur hexafluoride

Abstract is not available.

Thermal decomposition of titanyl oxalates II : Kinetics of decomposition of barium titanyl oxalate

Kinetics of the thermal decomposition of barium titanyl oxalate have been studied. Decomposition of the anhydrous oxalate is complex and deceleratory throughout. Kinetics of decomposition of the intermediate carbonate Ba2Ti2O5CO3 is greatly influenced by the thermal effects during its formation. The sigmoidal (α, t) curves obey a power law equation followed by first order decay. Presence of carbon in the vacuum prepared carbonate has a strong deactivating effect. Decomposition of the carbonate is accompanied by growth in particle size of the product, barium titanate.

Mossbauer effect studies of the thermal decomposition of iron(II) oxalate in hydrogen

Mössbauer-effect and X-ray studies were carried out on the product samples of the thermogravimetric analysis (TGA) and of the isothermal decomposition of iron(II) oxalate in flowing H2. Two types of sample configurations were employed for isothermal studies between 280 to 420°C for various periods of heating. Low temperature Mossbauer measurements at liquid nitrogen temperature were carried out to examine the superparamagnetic (SPM) contributions. From the spectra of samples decomposed at 340°C, in vertical experiments, the percentage SPM and percentage ferromagnetic (FM) area of Fe3O4 were estimated and an average size (˜167Å) for Fe3O4 was derived. Mossbauer measurements (at high temperatures) were carried out on Fe3C formed in horizontal experiments, for two samples decomposed at ˜320°C for 1 hr and 2 hr. An estimate of SPM and FM Fe3C was obtained by calculating KV, the anisotropy energy for the Fe3C in these two samples and values of 5.07 × 10−16 and 7.02 × 10−16 erg/sec, respectively, were obtained.

Storage stability of solid rocket fuels. 2. Effect of oxidizer loadings

Ageing behaviour, leading to ballistic changes, has been studied as a function of oxidizer loading in polystyrene/ammonium perchlorate solid-propellants. The ageing studies were carried out at 100 °C in air. Change in burning rate decreased as the oxidizer loading increased from 75 to 80%. The change in thermal decomposition rates both at 230 and 260 °C also decreased as the oxidizer loading in the propellants increased. The shapes of the plots of the changes in burning rate and thermal decomposition rate (230 and 260 °C) at different storage times for different oxidizer-loaded propellants seem to be exactly similar. These results lead to the conclusion that the thermal decomposition of the propellant may be responsible for bringing about the ballistic changes during the ageing process. Infrared studies of the binder portion of the aged propellant indicate that peroxide formation takes place during the course of ageing and that peroxide formation for a particular storage time and temperature increases as the loading decreases.

Thermal decomposition of hydrazinium monoperchlorate in the molten state

The thermal decomposition of hydrazinium monoperchlorate (HP-1) in the molten state has been investigated using differential thermal analysis, thermogravimetric analysis, a constant volume manometric technique and mass-spectrometry. The stoichiometry of the reaction can be represented by the equation: 20 N2H5C1O4 13 NH4C1O4 + 3.5 Cl2 + 2 O2 + 13 N2 + 0.5 N2O + 0.5 H2 + + 23.5 H2O The data seem to indicate that the mechanism, which involves an associated complex, remains unchanged from 140 to 190°. Consequently, impurities capable of forming associated complexes with the hydrazinium or the perchlorate ion desensitize the thermal decomposition of HP-1, the extent of desensitization being determined by the size, the charge and the concentration of the impurity.

Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate

Thermal decomposition of powdered ammonium perchlorate, catalysed by manganese dioxide (MnO2), has been studied in the low concentration ranges of the catalyst. MnO2 sensitises the thermal decomposition of ammonium perchlorate. The activation energy estimations of catalysed ammonium perchlorate show that the value is about 30 kcal/mol throughout the low and the high temperature regions whereas uncatalysed ammonium perchlorate gives two activation energies, 20 kcal/mol in the low temperature region (280-320°C) and 60 kcal/mol in the higher temperature region (350-390°C). This behaviour has been explained on the basis of an electron transfer process. The effectiveness of MnO2 in the thermal decomposition further increases on pre-heating the sample at 50°C for two weeks; manganese ions enter the ammonium perchlorate lattice during the process of pre-heating.

Delamination of Surfactant-Intercalated Brucite-Like Hydroxy Salts of Cobalt and Copper and Solvothermal Decomposition of the Resultant Colloidal Dispersions

Surfactant anion intercalated hydroxy salts of copper and cobalt of the formula M(OH)(2-x)(surf)(x)center dot mH(2)O [M = Cu, Co; surf = dodecyl sulfate. dodecyl benzene sulfonate. and x = 0.5 for Cu and 0.67 for Co] delaminate readily in 1-butanol to give translucent colloidal dispersions that are stable for months. The extent of delamination and the colloidal dispersion observed in these solids is higher than what had been observed for layered double hydroxides. The dispersions yield the corresponding nanoparticulate oxides on solvothermal decomposition. While the copper hydroxy salt forms similar to 300 nm dendrimer-like CuO nanostructures comprising nanorods of similar to 10 nm diameter, the cobalt analogue forms similar to 20 nm superparamagnetic particles of Co3O4.

Design of multiunit electronic exchanges through decomposition

In this paper, we exploit the idea of decomposition to match buyers and sellers in an electronic exchange for trading large volumes of homogeneous goods, where the buyers and sellers specify marginal-decreasing piecewise constant price curves to capture volume discounts. Such exchanges are relevant for automated trading in many e-business applications. The problem of determining winners and Vickrey prices in such exchanges is known to have a worst-case complexity equal to that of as many as (1 + m + n) NP-hard problems, where m is the number of buyers and n is the number of sellers. Our method proposes the overall exchange problem to be solved as two separate and simpler problems: 1) forward auction and 2) reverse auction, which turns out to be generalized knapsack problems. In the proposed approach, we first determine the quantity of units to be traded between the sellers and the buyers using fast heuristics developed by us. Next, we solve a forward auction and a reverse auction using fully polynomial time approximation schemes available in the literature. The proposed approach has worst-case polynomial time complexity. and our experimentation shows that the approach produces good quality solutions to the problem. Note to Practitioners- In recent times, electronic marketplaces have provided an efficient way for businesses and consumers to trade goods and services. The use of innovative mechanisms and algorithms has made it possible to improve the efficiency of electronic marketplaces by enabling optimization of revenues for the marketplace and of utilities for the buyers and sellers. In this paper, we look at single-item, multiunit electronic exchanges. These are electronic marketplaces where buyers submit bids and sellers ask for multiple units of a single item. We allow buyers and sellers to specify volume discounts using suitable functions. Such exchanges are relevant for high-volume business-to-business trading of standard products, such as silicon wafers, very large-scale integrated chips, desktops, telecommunications equipment, commoditized goods, etc. The problem of determining winners and prices in such exchanges is known to involve solving many NP-hard problems. Our paper exploits the familiar idea of decomposition, uses certain algorithms from the literature, and develops two fast heuristics to solve the problem in a near optimal way in worst-case polynomial time.

Correction of Ocular Artifacts in EEG Recordings using Empirical Mode Decomposition

EEG recordings are often contaminated with ocular artifacts such as eye blinks and eye movements. These artifacts may obscure underlying brain activity in the electroencephalogram (EEG) data and make the analysis of the data difficult. In this paper, we explore the use of empirical mode decomposition (EMD) based filtering technique to correct the eye blinks and eye movementartifacts in single channel EEG data. In this method, the single channel EEG data containing ocular artifact is segmented such that the artifact in each of the segment is considered as some type of slowly varying trend in the dataand the EMD is used to remove the trend. The filtering is done using partial reconstruction from components of the decomposition. The method is completely data dependent and hence adaptive and nonlinear. Experimental results are provided to check the applicability of the method on real EEG data and the results are quantified using power spectral density (PSD) as a measure. The method has given fairlygood results and does not make use of any preknowledge of artifacts or the EEG data used.

Carbon dynamics in peatlands under changing hydrology : Effects of water level drawdown on litter quality, microbial enzyme activities and litter decomposition rates

Pristine peatlands are carbon (C) accumulating wetland ecosystems sustained by a high water level (WL) and consequent anoxia that slows down decomposition. Persistent WL drawdown as a response to climate and/or land-use change directly affects decomposition: increased oxygenation stimulates decomposition of the old C (peat) sequestered under prior anoxic conditions. Responses of the new C (plant litter) in terms of quality, production and decomposability, and the consequences for the whole C cycle of peatlands are not fully understood. WL drawdown induces changes in plant community resulting in shift in dominance from Sphagnum and graminoids to shrubs and trees. There is increasing evidence that the indirect effects of WL drawdown via the changes in plant communities will have more impact on the ecosystem C cycling than any direct effects. The aim of this study is to disentangle the direct and indirect effects of WL drawdown on the new C by measuring the relative importance of 1) environmental parameters (WL depth, temperature, soil chemistry) and 2) plant community composition on litter production, microbial activity, litter decomposition rates and, consequently, on the C accumulation. This information is crucial for modelling C cycle under changing climate and/or land-use. The effects of WL drawdown were tested in a large-scale experiment with manipulated WL at two time scales and three nutrient regimes. Furthermore, the effect of climate on litter decomposability was tested along a north-south gradient. Additionally, a novel method for estimating litter chemical quality and decomposability was explored by combining Near infrared spectroscopy with multivariate modelling. WL drawdown had direct effects on litter quality, microbial community composition and activity and litter decomposition rates. However, the direct effects of WL drawdown were overruled by the indirect effects via changes in litter type composition and production. Short-term (years) responses to WL drawdown were small. In long-term (decades), dramatically increased litter inputs resulted in large accumulation of organic matter in spite of increased decomposition rates. Further, the quality of the accumulated matter greatly changed from that accumulated in pristine conditions. The response of a peatland ecosystem to persistent WL drawdown was more pronounced at sites with more nutrients. The study demonstrates that the shift in vegetation composition as a response to climate and/or land-use change is the main factor affecting peatland ecosystem C cycle and thus dynamic vegetation is a necessity in any models applied for estimating responses of C fluxes to changes in the environment. The time scale for vegetation changes caused by hydrological changes needs to extend to decades. This study provides grouping of litter types (plant species and part) into functional types based on their chemical quality and/or decomposability that the models could utilize. Further, the results clearly show a drop in soil temperature as a response to WL drawdown when an initially open peatland converts into a forest ecosystem, which has not yet been considered in the existing models.

Consideration on thermal decomposition of calcium hydroxide pellets for energy storage

The reversible chemical reaction of Ca(OH)2/CaO appears to be attractive for storage of solar thermal energy, in view of the nonpolluting and nontoxic nature of the reactants. This paper presents some data on thermal decomposition of calcium hydroxide pellets along with its additives of aluminum, aluminum hydroxide, zinc, and copper. The addition of aluminum and zinc powder enhanced the rate of decomposition considerably at 450°C, but copper had no effect. Considerations on the effect of additives are also discussed in some detail, though their effects are not established with certainty. There is some evidence that heat transfer into the pellet, and the number of potential nucleation sites due to thermal stresses, influence the kinetics and mechanism of decomposition.

Rare-earth chromium citrates as precursors for rare-earth chromites: lanthanum biscitrato chromium(III) dihydrate, La[Cr(C6H5O7)2]·2H

The thermal decomposition of lanthanum biscitrato chromium(III) dihydrate has been studied in static air and dynamic argon atmospheres. The complex decomposes in four steps: dehydration, decomposition of the citrate to an intermediate oxycarbonate, formation of LaCrO4(V) from oxycarbonate, and finally decomposition of LaCrO4(V) to LaCrO3. Formation of LaCrCrO4(V) requires the presence of oxygen The decomposition behaviour of a mechanical mixture of lanthanum citrate hydrate and chromium citrate hydrate was compared with that of the citrato complex. Both the starting material and the intermediates were characterized by X-ray diffraction, IR electronic and ESR spectroscopy, surface area and magnetic susceptibility measurements, as well as by chemical analysis. A scheme is proposed for the decomposition of lanthanum biscitrato chromium(III) dihydrate in air. LaCrO3 can be obtained at temperatures as low as 875 K by isothermal decomposition of the complex.