Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

The aggregation process in tetraethoxysilane-derived sonogels as an analogy to the critical phenomenon

The structural evolution in silica sols prepared from tetraethoxysilane (TEOS) sonohydrolysis was studied 'in situ' using small-angle x-ray scattering (SAXS). The structure of the gelling system can be reasonably well described by a correlation function given by gamma(r) similar to (1/R(2))(1/r) exp(- r/xi), where xi is the structure correlation length and R is a chain persistence length, as an analogy to the Ornstein-Zernike theory in describing critical phenomenon. This approach is also expected for the scattering from some linear and branched molecules as polydisperse coils of linear chains and random f-functional branched polycondensates. The characteristic length. grows following an approximate power law with time t as xi similar to t(1) (with the exponent quite close to 1) while R remains undetermined but with a constant value, except at the beginning of the process in which the growth of. is slower and R increases by only about 15% with respect to the value of the initial sol. The structural evolution with time is compatible with an aggregation process by a phase separation by coarsening. The mechanism of growth seems to be faster than those typically observed for pure diffusion controlled cluster-cluster aggregation. This suggests that physical forces (hydrothermal forces) could be actuating together with diffusion in the gelling process of this system. The data apparently do not support a spinodal decomposition mechanism, at least when starting from the initial stable acid sol studied here.

Knowledge-based spatiotemporal linear abstraction

We present a theoretical framework and a case study for reusing the same conceptual and computational methodology for both temporal abstraction and linear (unidimensional) space abstraction, in a domain (evaluation of traffic-control actions) significantly different from the one (clinical medicine) in which the method was originally used. The method, known as knowledge-based temporal abstraction, abstracts high-level concepts and patterns from time-stamped raw data using a formal theory of domain-specific temporal-abstraction knowledge. We applied this method, originally used to interpret time-oriented clinical data, to the domain of traffic control, in which the monitoring task requires linear pattern matching along both space and time. First, we reused the method for creation of unidimensional spatial abstractions over highways, given sensor measurements along each highway measured at the same time point. Second, we reused the method to create temporal abstractions of the traffic behavior, for the same space segments, but during consecutive time points. We defined the corresponding temporal-abstraction and spatial-abstraction domain-specific knowledge. Our results suggest that (1) the knowledge-based temporal-abstraction method is reusable over time and unidimensional space as well as over significantly different domains; (2) the method can be generalized into a knowledge-based linear-abstraction method, which solves tasks requiring abstraction of data along any linear distance measure; and (3) a spatiotemporal-abstraction method can be assembled from two copies of the generalized method and a spatial-decomposition mechanism, and is applicable to tasks requiring abstraction of time-oriented data into meaningful spatiotemporal patterns over a linear, decomposable space, such as traffic over a set of highways.

Thermal stability of the ‘cave’ mineral brushite CaHPO4•2H2O -mechanism of formation and decomposition

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the ‘cave’ mineral brushite. X-ray diffraction shows that brushite from the Jenolan Caves is very pure. Thermogravimetric analysis coupled with ion current mass spectrometry shows a mass loss at 111°C due to loss of water of hydration. A further decomposition step occurs at 190°C with the conversion of hydrogen phosphate to a mixture of calcium ortho-phosphate and calcium pyrophosphate. TG-DTG shows the mineral is not stable above 111°C. A mechanism for the formation of brushite on calcite surfaces is proposed, and this mechanism has relevance to the formation of brushite in urinary tracts.

Mechanism of the thermal decomposition of polystyrene peroxide

The thermal degradation of polystyrene peroxide was carried out using differential scanning calorimetry. The activation energy (E) was found to be 136 kJ mole–1 at all extents of decomposition. TheE value was found to correspond to-O-O-dissociation. The order of reaction was found to decrease from 2 to 1 as the decomposition progresse.

Combustion and Thermal Decomposition of Ammonium Perchlorate-Aluminium Composite Pellets: Mechanism for Aluminium Participation

Thermal behaviour of ammonium perchlorate-aluminium composites is studied using differential thermal analysis, thermogravimetry and differential scanning calorimetry. Electrical resistivity studies throw light on the mechanism of ammonium perchlorate decomposition at different aluminium contents. The differences observed in burning behaviour by earlier authors is explained in terms of porosity and thermal conductivity of the composite.

Kinetics and mechanism of thermal decomposition of tetramethylammonium nitrate

The mechanism of thermal decomposition of tetramethylammonium nitrate has been investigated by thermogravimetry and mass spectrometry. The activation energy for the decomposition has been determined by isothermal decomposition technique using thermogravimetry and by monitoring mass spectrometrically the formation of trimethylamine. The activation energies determined in both the cases compare well, suggesting that the decomposition proceeds via dissociation of tetramethylammonium nitrate into trimethylamine and methylnitrate.

The kinetics and mechanism of the thermal decomposition of sec-Butyl peroxide in liquid phase /|nby Sandor Szilagyi. -- 260 St. Catharines, Ont. : [s. n.],

Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

The kinetics and mechanism of the thermal decomposition of bis diphenyl methyl and related peroxides in liquid phase /|nby C. Thankachan. -- 260 St. Catharines, Ont. : [s. n.],

Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

Thermal decomposition of hydrotalcite with hexacyanoferrite(II) and hexacyanoferrate(III) anions in the interlayer : a controlled rate thermal analysis study

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrite(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites studied have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations based upon CRTA measurements show that 7 moles of water is lost, proving the formula of hexacyanoferrite(II) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.5 .7 H2O and for the hexacyanoferrate(III) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.66 * 9 H2O. Dehydroxylation combined with CN unit loss occurs in three steps between a) 310 and 367°C b) 367 and 390°C and c) between 390 and 428°C for both the hexacyanoferrite(II) and hexacyanoferrate(III) intercalated hydrotalcite.

Mechanism of dehydroxylation temperature decrease and high temperature phase transition of coal-bearing strata kaolinite intercalated by potassium acetate

The thermal decomposition and dehydroxylation process of coal-bearing strata kaolinite–potassium acetate intercalation complex (CSKK) has been studied using X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analysis, mass spectrometric analysis and infrared emission spectroscopy. The XRD results showed that the potassium acetate (KAc) have been successfully intercalated into coal-bearing strata kaolinite with an obvious basal distance increase of the first basal peak, and the positive correlation was found between the concentration of intercalation regent KAc and the degree of intercalation. As the temperature of the system is raised, the formation of KHCO3, KCO3 and KAlSiO4, which is derived from the thermal decomposition or phase transition of CSKK, is observed in sequence. The IR results showed that new bands appeared, the position and intensities shift can also be found when the concentration of intercalation agent is raised. The thermal analysis and mass spectrometric analysis results revealed that CSKK is stable below 300 °C, and the thermal decomposition products (H2O and CO2) were further proved by the mass spectrometric analysis. A comparison of thermal analysis results of original coal-bearing strata kaolinite and its intercalation complex gives new discovery that not only a new mass loss peak is observed at 285 °C, but also the temperature of dehydroxylation and dehydration of coal bearing strata kaolinite is decreased about 100 °C. This is explained on the basis of the interlayer space of the kaolinite increased obviously after being intercalated by KAc, which led to the interlayer hydrogen bonds weakened, enables the dehydroxylation from kaolinite surface more easily. Furthermore, the possible structural model for CSKK has been proposed, with further analysis required in order to prove the most possible structures.

Application of TG-FTIR to study SO2 evolved during the thermal decomposition of coal-derived pyrite

The thermal decomposition of the coal-derived pyrite was studied using thermogravimetry combining with Fourier-transform infrared spectroscopy (TG-FTIR) techniques to gain knowledge on the SO2 gas evolution process and formation mechanism during the thermal decomposition of the coal-derived pyrite. The results showed that the thermal decomposition of the coal-derived pyrite which started at about 400 ◦C was complete at 600 ◦C; the gas evolved can be established by combining the DTG peak, the Gram–Schmidt curve and in situ FTIR spectroscopic evolved gas analysis. It can be observed from the spectra that the pyrolysis products for the sample mainly vary in quantity, but not in species. It was proposed that the oxidation of the coal-derived pyrite started at about 400 ◦C and that pyrrhotite and hematite were formed as primary products. The SO2 released by the thermal decomposition of the coal-derived pyrite mainly occurred in the first pyrolysis stage between 410 and 470 ◦C with the maximum rate at 444 ◦C. Furthermore, the SO2 gas evolution and formation mechanism during the thermal decomposition of the coal-derived pyrite has been proposed.

Direct evidence for base-mediated decomposition of alkyl hydroperoxides (ROOH) in the gas phase

Alkyl hydroperoxides (ROOH) are attributed a key role in the biochemical oxidation of lipids during oxidative stress.1 In this chemistry ROOH compounds, where the R groups are unsaturated fatty acids, are viewed as transient ntermediates which are readily degraded, due to the lability of the RO-OH bond, to yield potentially genotoxic aldehydes and ketones.2 Generally, the decomposition of alkyl hydroperoxides is thought to be mediated by radical abstraction or electron transfer processes usually involving enzymes, transition metals, or recently, Vitamin C.3 In this paper we present the first unambiguous experimental and computational evidence for base-mediated heterolytic decomposition of simple alkyl hydroperoxides by the mechanism outlined in Scheme 1.