Study of the thermal decompositions of some transition metal perchlorates

The thermal decompositions of nickel(II), copper(II), cobalt(II) and manganese(II) perchlorates were studied by thermal analysis and kinetic measurements. Anhydrous perchlorates could not be prepared by heating and outgassing the samples in vacuum; oxides were obtained as the main solid decomposition products. In the case of cobalt and manganese perchlorates, oxidation of the metal ions was observed during the decomposition. In most cases the decompositions of the perchlorates followed the Avrami-Erofeyev kinetics. A correlation was found between the stabilities of the perchlorates and the effective field strengths of the cations.

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Zusammenfassung Die thermische Zersetzung von Nickel(II), Kupfer(II)-, Kobalt(II)- und Mangan(II)-perchloraten wurde mittels Thermoanalyse und kinetischer Messungen untersucht. Durch Erhitzen und Entgasen der Proben im Vakuum konnten keine wasserfreien Perchlorate hergestellt werden; Oxide wurden als feste Hauptzersetzungsprodukte erhalten. Im Falle der Perchlorate von Kobalt und Mangan wurde die Oxidation der Metallionen während der Zersetzung beobachtet. In den meisten Fällen verlief die Zersetzung der Perchlorate nach der Kinetik von Avrami-Erofeyev. Eine Korrelation wurde zwischen den Stabilitäten der Perchlorate und der tatsächlichen Feldstärke der Kationen gefunden.

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Résumé La décomposition thermique des perchloartes de nickel(II), de cuivre(II), cobalt(II) et de manganèse(II) a été étudiée par analyse thermique et mesures cinétiques. Les perchlorates anhydres n'ont pas pu être préparés par chauffage et traitement sous vide de échantillons; les oxydes ont été obtenus comme produits solides principaux de décomposition. Dans le cas des perchlorates de cobalt et de manganèse, l'oxydation des ions métalliques a été observée pendant la décomposition. Dans la plupart des cas, la décomposition des perchlorates a suivi la cinétique d'Avrami-Erofeyev. Une corrélation a été trouvée entre la stabilité des perchlorates et les intensités effectives des champs des cations.

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Disproportionation of some alkali metal chlorites in the solid phase

Thermal behaviours of some alkali metal chlorites were studied under dynamic and isothermal conditions and some physical data of the chlorites were also determined. It was found that these chlorites disproportionate into chlorate and chloride in the solid phase without any measurable evolution of gas. The disproportionations were strongly exothermic. The values of the activation energies for the disproportionation reactions were found to be much smaller than the dissociation energy required for the rupture of the Cl-O bond. It was concluded that the disproportionations of alkali metal chlorites take place by rearrangement inside the lattice, without formation of atomic oxygen.

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Zusammenfassung Das thermische Verhalten einiger Alkalimetallchlorite wurde unter dynamischen und isothermen Bedingungen untersucht und einige physikalischen Daten der Chlorite bestimmt. Es wurde festgestellt, da\ diese Chlorite in fester Phase ohne me\bare Gasentwicklung zu Chloraten und Chloriden disproportionieren. Der Disproportionierungsvorgang war streng exotherm. Die für die Disproportionierungsreaktion festgestellten Werte der Aktivierungsenergie waren viel niedriger als die zur Spaltung der Bindung Cl-O benötigte Dissoziationsenergie. Es wurde gefolgert, da\ die Disproportionierung von Alkalimetallchloriten durch Umordnung im Inneren des Gitters ohne Bildung von atomarem Sauerstoff erfolgt.

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Résumé Le comportement thermique de chlorites de métaux alcalins a été étudié en conditions de chauffage dynamique et isotherme. Quelques données physiques des chlorites ont aussi été déterminées. Il a été observé que ces chlorites se dismutent en phase solide en chlorate et chlorure sans dégagement mesurable de gaz. La dismutation est fortement exothermique. Les valeurs des énergies d'activation de la réaction de dismutation sont bien inférieures à l'énergie de dissociation nécessaire à la rupture de la liaison Cl-O. On en conclut que la dismutation des chlorites des métaux alcalins s'effectue par réarrangement à l'intérieur du réseau sans formation d'oxygène atomique.

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We thank Miss E. Szcs for assistance in the experimental work.     

Large Cliques in -Free Graphs

Dedicated to the memory of Paul Erdős A graph is called -free if it contains no cycle of length four as an induced subgraph. We prove that if a -free graph has n vertices and at least edges then it has a complete subgraph of vertices, where depends only on . We also give estimates on and show that a similar result does not hold for H-free graphs––unless H is an induced subgraph of . The best value of is determined for chordal graphs. Received October 25, 1999 RID="*" ID="*" Supported by OTKA grant T029074. RID="**" ID="**" Supported by TKI grant stochastics@TUB and by OTKA grant T026203.     

Application of a sulphide-selective electrode in the absence of a pH-buffer

Calibration of a sulphide electrode in the pH-range 9-12 has been studied as an e.m.f. vs. (pH - p[HS(-)]) function by measuring e.m.f. and pH in parallel. Calibration can also be done in this pH range by using a differential amplifier with a three-electrode measuring cell (glass, sulphide-selective and reference electrodes). The effects of an antioxidant (ascorbic acid) and a complexing agent (DCTA) on the calibration of the glass-sulphide electrode cell at pH < 5 were studied. The applicability of this end-point indicator cell has been demonstrated for titrations of Ag(+), Pb(2+) and Bi(3+) with Na(2)S.     

Roth-type theorems in finite groups

We prove Roth-type theorems in finite groups. Our main tool is the Triangle Removal Lemma of Ruzsa and Szemerédi.     

Incidence Theorems for Pseudoflats

We prove Pach-Sharir type incidence theorems for a class of curves in Rⁿ and surfaces in R³, which we call pseudoflats}. In particular, our results apply to a wide class of generic irreducible real algebraic sets of bounded degree.     

Method for independent control of particle size and distance in rhodium epitaxy on TiO2(110)-(1×2) surface An STM study

A method for independent control of the particle size and distance is presented for rhodium epitaxy on TiO₂(110)-(1×2) surface. The real space imaging of the surface morphology was performed by scanning tunneling microscopy. The amount of the deposited rhodium was checked by Auger electron spectrometry. The method consists of two steps: (i) evaporation of 0.001–0.050 ML equivalent of rhodium at room temperature with a post-annealing at 1100 K (“seeding”); (ii) post-deposition of rhodium for growing of the Rh nanoparticles formed in step (i) (“growing”). The mechanism of this procedure is based on the large difference of the surface diffusion coefficient between Rh adatoms and Rh nanocrystallites larger than 1–2 nm. In the first step the average distance between the metal particles is controlled in the range 5–200 nm, the second step determines the particles size (2–50 nm). This work demonstrates that the diffusion processes of metal nanoparticles of different sizes and the growing modes of the crystallites can be studied in detail by application of seeded surfaces.     

Effects of preadsorbed oxygen on the formation and decomposition of NCO on Rh(111) surfaces

The interaction of HNCO with oxygen dosed Rh(111) surface has been investigated by Auger electron, electron energy loss and thermal desorption spectroscopy. The presence of adsorbed oxygen exerted no apparent influence on the weakly adsorbed HNCO (T_p = 130 K). It promoted, however, the dissociative adsorption of HNCO by forming a strong O—H bond which prevented the associative desorption of HNCO. As a result no H₂ and NH₃ formation occurred, in contrast with the clean surface, and the surface concentration of irreversibly bonded NCO was also increased. New products of the surface reaction were H₂O and CO₂, in addition to CO and N₂ observed on a clean surface. From the behavior of the losses characteristic for the adsorbed NCO it appeared that the preadsorbed oxygen exerted a significant stabilizing effect on the NCO bonded to the Rh.     

Dissociation of CO on supported Rh

The adsorption and dissociation of CO have been investigated on alumina supported Rh at atmospheric pressure. The dissociation of CO was detected above 473 K. The carbon formed reacted with H₂ even at 300–473 K yielding CH₄. A significant aging of surface carbon occurred above 573 K.     

Collinear Points in Permutations

Consider the following problem: how many collinear triples of points must a transversal of have? This question is connected with venerable issues in discrete geometry. We show that the answer, for n prime, is between (n − 1)/4 and (n − 1)/2, and consider an analogous question for collinear quadruples. We conjecture that the upper bound is the truth and suggest several other interesting problems in this area.Received August 29, 2004