Reduction with Phase Change

Dutartre, M. Primet, and G.-A. Martin, Reaction Kinetics and Catalysis Letters, 1975, 3, 249. 

A carbon of specific bridging function has been claimed to form if nickel oxide is treated with n-hexane or cyclohexane before reduction with hydrogen. The priming of the reduction increases not only the number of nuclei but also their subsequent rate of growth, and it is proposed that nickel with finely divided and admixed carbon is formed in intimate contact with the nickel oxide during attack by the hydrocarbon. The very small particles of nickel produced dissolve 

A Mdssbauer investigation of the reduction of iron oxide (0.05 wt % Fe) and iron-oxide-with-palladium (0.05 wt % Fe, 2.2 wt % Pd), carried upon 7 -Al203, reveals that supported ferric ion alone, under hydrogen, yields ferrous ion only at 500—700 °C this reduction takes place at room temperature with the bimetallic catalyst and proceeds to form a PdFe alloy at 500 °C. Similar effects are found in reduction by carbon monoxide, which yields iron-palladium metal clusters at 400 °C. The view is taken that migration over T7-A1203 is not involved but that activated hydrogen transfers only at bridgeheads on the contact line between the metal and iron oxide. 

Tournayan, R. Frety, H. Charcosset, and Y. Trambouze, Jnd. chim. beige, 1973,38, 496. R. Frety, L. Tournayan, and H. Charcosset, Ann. Chim France), 1974, 9, 341 S T Rostovtsev, V. G. Bel chenko, and V. K. Simonov, Termodin. Kinet. Protsessov Vosstanov Metal. Mater. Konf., 1972, 70. 

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In the test period Feb.—April 84, in which the temperature of the slurry in the tanks was lower than 7°C, during the first 2 months (it in creased to 17°-18°C only during the final phase), changes in the parameters under observation were less marked, except in the tank where aeration had been carried out. In this predominantly winteiy testing period, further reductions in the various parameters were observed after the tanks had been filled. The C.O.D. for example was reduced by 20% in the tank without treatment by 30% in the one with agitation and by 50% in the aerated tank. 

Aluminum nitride UFPs have been synthesized by thermal decomposition from many kinds of precursor such as polyminoalanef l/ ) AIH(NR)] (50), aluminum polynuclear complexes of basic aluminum chloride (BAC) or basic aluminum lactate (BAL) (51), and (hydroxo)(succinato) aluminum(lll) complex, A1(0H)(C4H404) jfLO (52). These precursors were calcined under N2 or NH, gas flow. The calcination temperatures, which depend on the individual precursor, can be lower by 600-200°C than the 1700°C in ihe conventional carbothermal reduction method. The XRD measurements at intermediate stages of the calcination process showed the phase change from an amorphous state to a trace of y-alumina with very fine grains and finally to wurtzite-type AIN (51,52). Lowering the calcination... 

Copper acetate was used in Ref. 38 it was noted that if chloride was used instead of acetate, no deposition occurred, and this was attributed to adsorption of chloride on the substrate (Pt). The berzelianite phase with a small amount of umangite impurity was obtained. The composition and phase of the film could be altered by electrochemical cathodic polarization (in an aqueous K2SO4 solution). Initially, there occurred an increase in lattice parameters and decrease in x (Cu2-A Se). With continued polarization, a phase change occurred until eventually only orthorhombic Cui xSe was present in the film. The umangite phase also disappeared, and it was believed that this impurity phase catalyzed the phase transformation. The change in composition during cathodic polarization was attributed to reduction of zerovalent Se to Se, which was dissolved in the solution. Based on the study of Fohner and JeUinek [41] discussed earlier, this explanation can be interpreted as reduction of Sei ( monovalent Se) to Se (divalent Se). 

Thermal Properties. A typical dsc thermogram of an HPL/PVA blend (Fig. 4) shows a single Tg and Tm (10). Differences in the shape of the melting endotherms of PVA(96), (88), and (75) can be attributed to different degrees of crystallinity in the three polymers. Changes in crystalline structure of polymer blends usually result from polymer-polymer interactions in the amorphous phase. Such interactions result in a reduction of crystallinity, thereby reducing the enthalphy of the phase change (16,17). The observed reductions in melt endotherm area of HPL blends with PVA (> 0) may therefore indicate the existence of polymer-polymer interactions between the two types of macromolecules. 

Aykan (35) reported that ammoxidation of propylene occurred over a silica-supported bismuth molybdate catalyst in the absence of gas-phase oxygen, although the catalytic activity decreased rapidly with increasing catalyst reduction. The reduction process was followed by X-ray and it was found that phase changes which occurred in the catalyst and the decrease in catalytic activity corresponded quantitatively to the depletion of lattice oxygen. 

Expected Range of pH Values. Changes in solution pH in rock-water systems may result from two primary causes. The first cause is due to changes in equilibrium constants with variation in temperature and pressure. For example, the neutral pH of pure water changes from 7.00 at 20°C to approximately 5.6 at 200°C and 300 bars pressure due to changes in the value of the dissociation constant for water. Precipitation, dissolution, oxidation, or reduction of phases with consumption or generation of hydrogen ion is the second primary cause of pH variation. 

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