Investigation of the anodic decomposition of the solid electrolyte RbCu4Cl3I2

The process of electrochemical decomposition of the solid electrolyte RbCu₄Cl₃I₂ at a vitreous carbon electrode has been investigated. The anodic decomposition of the electrolyte occurs in two steps. At first, the oxidizing electrode reaction of Cu⁺ ions to Cu²⁺ ions takes place at potentials higher than 0.57 V and a layer of decomposition products is formed on the electrode surface, including the divalent copper compound RbCuCl₃. Then the oxidizing reaction of I^– ions occurs at potentials higher than approximately 0.67 V, with deposition of an iodine layer onto the electrode surface. The deposition rate of the layers of decomposition products is controlled by instantaneous nucleation and two-dimensional growth of the deposit. The total thickness of the passivating layer of decomposition products on the anode is equal to ca. 1 μm. Electronic Publication     

Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Polarization characteristics of electromembrane systems (EMS) based on the Russian commercial heterogeneous membranes MA-40 and MA-41, the anion-exchange heterogeneous membrane AMH (Mega, Czech Republic), and the modified membrane MA-40M are studied by the method of rotating membrane disk in dilute sodium chloride solutions. The effective transport numbers of ions are found; the partial voltammetric characteristics (VAC) with respect to chloride and hydroxyl ions are measured; the limiting current densities are calculated as a function of the membrane disk rotation rate. In terms of the theory of the overlimiting state of EMS, based on experimental VAC and the dependences of the effective transport numbers on the current density, the following internal parameters of systems under study are calculated: the space charge and electric field strength distribution over the diffusion layer and the membrane. It is shown that water dissociation can be virtually completely eliminated by substituting chemically stable quaternary ammonium groups inert with respect to water dissociation in the surface layer of a heterogeneous anion-exchange membrane MA-40 for the active ternary and secondary functional amino groups. The maximum electric field strength values at the membrane/solution interface, which were found in the framework of the theory of over-limiting state, turned out to be close for all anion-exchange membranes studied, namely, (7?C9) × 10⁶ V/cm. This suggests that it is the nature of ionogenic groups in the surface layer rather than the field effect that plays the decisive role in the membrane ability to accelerate the water dissociation reaction. It is proved experimentally that in highly intense current modes of the electrodialysis process, the thermal hydrolysis of quaternary ammonium bases occurs in strongly basic MA-41 and AMH membranes by the Hofmann reaction to form ternary amino groups catalytically active in water dissociation reaction. Based on the concept on the catalytic mechanism of water dissociation, the fraction of ternary amino groups formed by thermal hydrolysis in the surface layer (the space charge region) of monopolar anion-exchange membranes MA-41 and AMH is assessed quantitatively as 0.7 and 6.5%, respectively.     

Efficient subnanometric gold-catalyzed hydrogen generation via formic acid decomposition under ambient conditions

Formic acid (FA) has tremendous potential as a safe and convenient source of hydrogen for sustainable chemical synthesis and renewable energy storage, but controlled and efficient dehydrogenation of FA by a robust solid catalyst under ambient conditions constitutes a major challenge. Here, we report that a previously unappreciated combination of subnanometric gold and an acid-tolerant oxide support facilitates the liberation of CO-free H(2) from FA. Applying an ultradispersed gold catalyst comprising TEM-invisible gold subnanoclusters deposited on zirconia to a FA-amine mixture affords turnover frequencies (TOFs) up to 1590 per hour and a turnover number of more than 118,400 at 50 °C. The reaction was accelerated at higher temperatures, but even at room temperature, a significant H(2) evolution (TOFs up to 252 h(-1) after 20 min) can still be obtained. Preliminary mechanistic studies suggest that the reaction is unimolecular in nature and proceeds via a unique amine-assisted formate decomposition mechanism on Au-ZrO(2) interface.     

The anodic behaviour of zinc in flowing electrolyte systems

The current-time behaviour has been calculated for successive two dimensional nucleation under potentiostatic conditions. Using numerical integration the contributions due to the first 50 layers have been found and the steady state behaviour has been estimated.     

A platinum-like behavior electrocatalyst and solid polymer electrolyte technique used on high concentration of electrochemical ozone water generation

This study presents an advanced ozone production process using the solid polymer electrolyte (SPE) technique, similar to the fabrication of proton exchange membrane fuel cell (PEMFC) membrane electrode assembly (MEA). Tungsten carbide and platinum on carbon black are coated on anode and cathode sides of a polymer membrane (Du Pont), respectively, to produce high concentration of ozone water. The water electrolysis of ozone generation requires a higher voltage than that of hydrogen production. On one hand, tungsten carbide, which is a platinum-like behavior electrocatalyst, plays a key role in preventing the MEA from corroding or oxidizing under high voltage. On the other hand, the carbon paper is replaced by a titanium porous disc to bear higher voltage. Moreover, an outstanding electronic control system can produce 1.37 ppm ozone water at atmosphere by adjusting the voltage range (6–10 V) with a current set to the maximum of 3 A for a household demand of ozone water generation.     

Formation of anodic TiO2 nanotube or nanosponge morphology determined by the electrolyte hydrodynamic conditions

The present work studies the effect of hydrodynamic conditions on the growth of anodic TiO₂ nanostructures on Ti in a glycerol/water/NH₄F electrolyte. Parameter screening for fluoride content, anodization voltage and rotation rate (Reynolds number) of a rotating anode showed that two distinctly different TiO₂ morphologies could be obtained: the classic ordered nanotubes or a nanoscale sponge layer. We present conditions for TiO₂ sponge formation and growth to several micrometers of thickness, and show that in specific cases sponge layers can be superior to tube morphologies, as illustrated for photoelectrochemical water-splitting under standard AM 1.5 conditions.     

Kinetic of sorbitol decomposition under non-isothermal conditions

The thermal behavior of sorbitol was studied under non-isothermal conditions, in both air and nitrogen atmosphere. The main process is a deep and continuous dehydration. For the kinetic analysis, the TG/DTG data obtained at five heating rates were processed by three different methods: Friedman, Budrugeac-Segal and non-parametric kinetic, respectively. This analysis indicates a complex reaction with a preponderant chemical process, described by a conversion function (1−α)^3/2, accompanied by diffusion.     

The gas-phase decomposition of methylsilane. Part I. Mechanism of decomposition under shock-tube conditions

The gas-phase decompositions of methylsilane and methylsilane-d₃ have been investigated in a single-pulse shock tube at 4700 torr total pressure in the temperature range of 1125–1250 K. For CH₃SiD₃ at 1200 K three primary steps occur in the homogeneous decomposition with efficiencies in parentheses: , , and . For CH₃SiH₃ at 1200 K the primary CH₄ elimination efficiency is 0.09 while the total primary H₂ elimination efficiency is 0.91. Minor product formations of C₂H₄, acetylene, dimethylsilane, and SiH₄ are discussed.     

Radiation-induced decomposition of PETN and TATB under extreme conditions

We conducted a series of experiments investigating decomposition of secondary explosives PETN and TATB at varying static pressures and temperatures using synchrotron radiation. As seen in our earlier work, the decomposition rate of TATB at ambient temperature slows systematically with increasing pressure up to at least 26 GPa but varies little with pressure in PETN at ambient temperature up to 15.7 GPa, yielding important information pertaining to the activation complex volume in both cases. We also investigated the radiation-induced decomposition rate as a function of temperature at ambient pressure and 26 GPa for TATB up to 403 K, observing that the decomposition rate increases with increasing temperature as expected. The activation energy for the TATB reaction at ambient temperature was experimentally determined to be 16 +/- 3 kJ/mol.     

The gas-phase decomposition of methylsilane. Part II. Mechanisms of decomposition under static system conditions

The static system pyrolysis of methylsilane (T ～ 700 K, P_T ～ 150 torr), pure and in the presence of ethylene, propylene, and acetylene, has been investigated. It is proposed that in the uninhibited system, the major products (silane and dimethylsilane) are produced by free radical processes, and that the free radicals are formed at the walls from methylsilylenes. In the presence of olefins, the free radicals are trapped to form methylsilane adducts. In acetylene, trapping of methylsilylenes prevents free radical production and eliminates the free radical produced products of the pure and the olefin inhibited systems. Rates of initiation correlate with rates of reactant loss in acetylene inhibited systems, and with rates of hydrogen formation in olefin inhibited systems. Rough estimates of primary dissociation process yields give for the 1,1-H₂ elimination ?_1,1 ? 0.78, for the 1,2-H elimination ?_1,2 ? 0.16, and for the methane elimination ?CH₄ ? 0.06 at 700 K. Deuteration lowers initial step kinetics by about 15%.     

On the anodic decomposition of the zinc selenide electrode

The electrochemical decomposition of n-type zinc selenide has been studied in connection with the chemisorption of the OH^? groups onto the semiconductor surface, depending on the band bending. The influence of oxidizing agents such as the illumination of the electrode or the presence of ferricyanide ions in the solution, leading to injection of holes into the valence band, has also been put in evidence. In contrast with the usual decomposition models that are rather simple, a complex and multistep mechanism is proposed here in order to account for the different observations made on these electrodes: the triangular decomposition pits, the deep red layer of amorphous selenium and the bright grey layer of zinc oxide.     

TG and TGT investigations of the decomposition of nitrocellulose under quasi-isothermal conditions

A derivatographic study was made of the influence of the slow heat transport between the sample and its surroundings upon the courses of exothermic transformations. It was found that if the sample was placed in a thin film layer on the multiplate sample holder and the quasi-isothermal heating technique was applied, then the rate of the decomposition could already be regulated at will, up to a certain limit. Under the conventional thermoanalytical conditions the same sample decomposed in an explosion-like way. The examinations were supplemented with thermo-gas-titrimetric (TGT) measurements.

---

Zusammenfassung Die Autoren untersuchten mit dem Derivatographen die Wirkung der langsamen Wärmeübertragung zwischen Probe und Umgebung auf den Verlauf exothermer Umwandlungen. Es wurde festgestellt, daß bei Auftragung der Probe in einer dünnen Filmschicht auf den Mehrplatten-Probenbehälter und bei Anwendung einer quasi-isothermen Aufheiztechnik die Zersetzungsgeschwindigkeit bis zu einer gewissen Grenze bereits nach Belieben gesteuert werden kann. Dieselbe Probe wird unter den üblichen thermoanalytischen Bedingungen explosionsartig zersetzt. Die Autoren ergänzten ihre Prüfungen auch mit thermogas-titrimetrischen (TGT) Messungen.

---

Résumé Les auteurs ont étudié à l'aide d'unDerivatograph l'influence du transfert de chaleur lent entre l'échantillon et son environnement, sur l'allure des transformations exothermiques. Les résultats montrent que si l'échantillon est placé sous forme de films minces sur le support multiplaques et s'il est chauffé en régime quasi-isotherme, la vitesse de la décomposition peut-être contrôlée, jusqu'à une certaine limite, à volonté. Si l'on applique les conditions habituelles de l'analyse thermique, le même échantillon se décompose de manière explosive. Les auteurs ont complété leurs études en effectuant également l'analyse titrimétrique des gaz émis.

---

, . , - - , . . -- ().

---

---

The authors wish to thank Prof. E. Pungor for valuable discussions.     

Computational study of the oxidation and decomposition of dibenzofuran under atmospheric conditions

The atmospheric degradation of dibenzofuran (DF) initiated by OH addition has been studied by using density functional theory (B3LYP method). Site C1 in DF is predicted to be the favored site for OH addition, with a branching ratio of 0.61 to produce a DF-OH(1) adduct. The calculated reaction rate constant for OH addition to DF has been used to predict the atmospheric lifetime of DF to be 0.45 day. Three different modes of attack of O2 ((3)Sigma(g)) on DF-OH(1) have been examined. Abstraction of hydrogen gem to OH in DF-OH(1) by O2 ((3)Sigma(g)) (producing 1-dibenzofuranol I) and dioxygen addition in the three radical sites in cis and trans orientation (relative to the ispo-added OH) of the pi-delocalized electron system of DF-OH(1) are feasible under atmospheric conditions. The free energy of activation (at 298.15 K) for the formation of 1-dibenzofuranol is 15.1 kcal/mol with a free energy change of -36.3 kcal/mol, while the formation of DF-OH(1)-O2 adducts are endergonic by 9.2-21.8 kcal/mol with a 16.3-23.6 kcal/mol free energy of activation. On the basis of the calculated reaction rate constants, the formation of 1-dibenzofuranol is more important than the formation of DF-OH-O2 adducts. The results presented here are a first attempt to gain a better understanding of the atmospheric oxidation of dioxin-like compounds on a precise molecular basis.     

Thermal decomposition of the magnesium sulphate hydrates under quasi-isothermal and quasi-isobaric conditions

In the course of thermal decomposition of the magnesium sulphate hydrates MgSO₄.nH₂O (n=7; 6; 5; 4; 3; 2; 5/4; 1) the intermediate steps MgSO₄.3H₂O, MgSO₄.2H₂O, MgSO₄.H₂O and — MgSO₄ are observed under quasi-isothermal and quasi-isobaric conditions atp 0.1 MPa dependent on the water contents. The structure of the obtained monohydrate phase is identical with that of kieserite. Thermal decomposition of the magnesium sulphate hydrates is essentially influenced by the water vapour partial pressure.

---

Zusammenfassung Beim thermischen Abbau der Magnesiumsulfathydrate MgSO₄.nH₂O (n=7; 6; 5; 4; 3; 2; 5/4; 1) unter quasiisothermen- und quasiisobaren Bedingungen werden bei p–0.1 MPa, in AbhÄngigkeit von den Wassergehalten, die Zwischenstufen MgSO₄.3H₂O; MgSO₄.2H₂O; MgSO₄.H₂O sowie-MgSO₄ beobachtet. Die erhaltene Monohydratphase ist strukturell mit Kieserit identisch. Der thermische Abbau der Magnesiumsulfathydrate wird wesentlich vom Wasserdampfpartialdruck beeinflu\t.

---

---

We gratefully acknowledge the assistance of Dr. K. Köhnke in providing X-ray diffraction investigations and the scanning electron micrographs provided by Dr. Ulrich, Bergakademie Freiberg.     

Kinetic of decomposition of some complexes under non-isothermal conditions

Kinetics of thermal decomposition of three structurally similar complexes Co₂Cu(C₂O₄)₃ (R-diam)₂, where R is ethyl, 1,2-propyl or 1,3-propyl, was studied under non-isothermal conditions and nitrogen dynamic atmosphere at heating rates of 5, 7, 10, 12 and 15 K min⁻¹. For data processing the Flynn-Wall-Ozawa and a modified non-parametric kinetic methods were used. By both methods the activation energy are in the range of 97–102 kJ mol⁻¹. The formal kinetic is r=kα(1−α)². Also a compensation effect between lnA and E was evidenced. The kinetic analysis lead to the conclusion of an identic decomposition mechanism by a single step process.     

Unexpected photolytic decomposition of alkyl azides under mild conditions

Alkyl azides have been found to undergo an unexpectedly facile photodecomposition under mild conditions (laboratory light) and the reaction gives rise to small amounts of aldehydes and monoacyl aminal rearrangement products that can dramatically impact on the uses of azides in chemistry, biology and medicine.     

Self-assembly of alkylthiosulfates on gold: role of electrolyte and trace water in the solvent

Spontaneous self-assembly of alkylthiosulfates on gold produce monolayers similar to the corresponding alkanethiols. Alkylthiosulfate self-assembly from THF solutions is inhibited in the presence of tetrabutylammonium tetrafluoroborate electrolyte. The mechanism of alkylthiosulfate self-assembly and the role of electrolyte and trace water in the solvent are investigated using open-circuit potential measurements, contact angle goniometry and redox electron transfer blocking experiments to explore the hypothesis that trace water present in the solvent facilitates monolayer formation on gold. Furthermore, the unique behavior of tetrabutylammonium tetrafluoroborate, compared to other tetrabutylammonium electrolytes, on the inhibition of alkylthiosulfate self-assembly has been explained.