scholarly journals The oxidation of copper and the reactions of hydrogen and carbon monoxide with copper oxide

An investigation has been made of the activation of copper by successive oxidation and reduction with hydrogen. Reduction with carbon monoxide causes deactivation of the surface. The heats of adsorption of carbon monoxide and oxygen and the heat liberated during the catalytic reaction of carbon monoxide and oxygen on a cuprous oxide film formed on metallic copper have been measured at room temperature. The kinetics of the reactions have been studied. The electrical conductivity of thin films of oxides has been measured during the reduction with hydrogen, and a study made of the process of embrittlement, whereby the surface is activated. The effect of the adsorption of gases on the conductivity of the Cu 2 O-CuO surface has been investigated. Oxygen enhances the conductivity and carbon monoxide and hydrogen depress it. The reaction between carbon monoxide and oxygen has been followed at room temperature by conductivity measurements and the results have been employed to interpret the nature of the adsorption, the kinetics of the reaction, and the deactivation of the surface by carbon monoxide.

1969 ◽  
Vol 22 (7) ◽  
pp. 1341 ◽  
Author(s):  
MW Anker ◽  
R Colton ◽  
CJ Rix ◽  
IB Tomkins

Compounds of the general formulae M(CO)3(dpe)X2, [M(CO)2(dpe)1.5X2]2, and M(CO)2(dpe)2X2 have been prepared and characterized (M = Mo, W; dpe = bis- (1,2-diphenylphosphino)ethane; X = Cl, Br, I). All of the compounds are diamagnetic and most of them are non-electrolytes. However, conductivity measurements indicate that, for the iodo derivatives only, the bis(dpe) compounds should be formulated as 1 : 1 electrolytes, [M(CO)2(dpe)2I]I. ��� For the iodo series of compounds only, there is a complex series of reversible reactions including a new type of carbon monoxide carrying system. In addition, the dimeric dpe derivatives are cleaved by carbon monoxide at room temperature and pressure to give equal quantities of [M(CO)2(dpe)2I]I and M(CO)3(dpe)I2.


The catalytic reaction has been studied on a granular surface of the metal coated with cuprous oxide. The nature of the adsorbed species in the stationary state of the reaction has been investigated by measurements of heats of adsorption and by B. E. T. measurements. The adsorption characteristics of cuprous oxide have been compared with those of cupric oxide, and some measurements have been made of the heats of adsorption of hydrogen, ethylene and sulphur dioxide on cuprous oxide. The differential heat of adsorption of oxygen during the formation of the first few layers of cuprous oxide on copper metal has been determined. A constant value of 55 kcal is obtained after the first few layers have been built up. The adsorbed oxygen reacts with carbon monoxide and dioxide, giving a CO 3 complex as an intermediate stage in the reactions. The properties of this complex have been studied by calorimetric methods and it has been shown to be unstable in the presence of carbon monoxide. The reactivity of the adsorbed oxygen decreases with time, and it is concluded that this is due to the diffusion of Cu + ions to the surface, which partially builds the oxygen ions into the lattice. The steps in the reaction mechanism of the catalytic reaction have been formulated, and it is shown that in the stationary state carbon monoxide, oxygen ions and a C0 3 complex are present on the surface, the last two species being present in small amount. An explanation is given of the dependence of the reaction on the oxygen pressure.


Author(s):  
Bradley L. Thiel ◽  
Chan Han R. P. ◽  
Kurosky L. C. Hutter ◽  
I. A. Aksay ◽  
Mehmet Sarikaya

The identification of extraneous phases is important in understanding of high Tc superconducting oxides. The spectroscopic techniques commonly used in determining the origin of superconductivity (such as RAMAN, XPS, AES, and EXAFS) are surface-sensitive. Hence a grain boundary phase several nanometers thick could produce irrelevant spectroscopic results and cause erroneous conclusions. The intergranular phases present a major technological consideration for practical applications. In this communication we report the identification of a Cu2O grain boundary phase which forms during the sintering of YBa2Cu3O7-x (1:2:3 compound).Samples are prepared using a mixture of Y2O3. CuO, and BaO2 powders dispersed in ethanol for complete mixing. The pellets pressed at 20,000 psi are heated to 950°C at a rate of 5°C per min, held for 1 hr, and cooled at 1°C per min to room temperature. The samples show a Tc of 91K with a transition width of 2K. In order to prevent damage, a low temperature stage is used in milling to prepare thin foils which are then observed, using a liquid nitrogen holder, in a Philips 430T at 300 kV.


Author(s):  
Harry A. Atwater ◽  
C.M. Yang ◽  
K.V. Shcheglov

Studies of the initial stages of nucleation of silicon and germanium have yielded insights that point the way to achievement of engineering control over crystal size evolution at the nanometer scale. In addition to their importance in understanding fundamental issues in nucleation, these studies are relevant to efforts to (i) control the size distributions of silicon and germanium “quantum dots𠇍, which will in turn enable control of the optical properties of these materials, (ii) and control the kinetics of crystallization of amorphous silicon and germanium films on amorphous insulating substrates so as to, e.g., produce crystalline grains of essentially arbitrary size.Ge quantum dot nanocrystals with average sizes between 2 nm and 9 nm were formed by room temperature ion implantation into SiO2, followed by precipitation during thermal anneals at temperatures between 30°C and 1200°C[1]. Surprisingly, it was found that Ge nanocrystal nucleation occurs at room temperature as shown in Fig. 1, and that subsequent microstructural evolution occurred via coarsening of the initial distribution.


1977 ◽  
Vol 16 (01) ◽  
pp. 30-35 ◽  
Author(s):  
N. Agha ◽  
R. B. R. Persson

SummaryGelchromatography column scanning has been used to study the fractions of 99mTc-pertechnetate, 99mTcchelate and reduced hydrolyzed 99mTc in preparations of 99mTc-EDTA(Sn) and 99mTc-DTPA(Sn). The labelling yield of 99mTc-EDTA(Sn) chelate was as high as 90—95% when 100 μmol EDTA · H4 and 0.5 (Amol SnCl2 was incubated with 10 ml 99mTceluate for 30—60 min at room temperature. The study of the influence of the pH-value on the fraction of 99mTc-EDTA shows that pH 2.8—2.9 gave the best labelling yield. In a comparative study of the labelling kinetics of 99mTc-EDTA(Sn) and 99mTc- DTPA(Sn) at different temperatures (7, 22 and 37°C), no significant influence on the reduction step was found. The rate constant for complex formation, however, increased more rapidly with increased temperature for 99mTc-DTPA(Sn). At room temperature only a few minutes was required to achieve a high labelling yield with 99mTc-DTPA(Sn) whereas about 60 min was required for 99mTc-EDTA(Sn). Comparative biokinetic studies in rabbits showed that the maximum activity in kidneys is achieved after 12 min with 99mTc-EDTA(Sn) but already after 6 min with 99mTc-DTPA(Sn). The long-term disappearance of 99mTc-DTPA(Sn) from the kidneys is about five times faster than that for 99mTc-EDTA(Sn).


2009 ◽  
Vol 59 (12) ◽  
Author(s):  
Mihai Contineanu ◽  
iulia Contineanu ◽  
Ana Neacsu ◽  
Stefan Perisanu

The radiolysis of the isomers L-, D- and DL- of the aspartic acid, in solid polycrystalline state, was investigated at room temperature. The analysis of their ESR spectra indicated the formation of at least two radicalic entities. The radical, identified as R3, resulting from the deamination of the acid, exhibits the highest concentration and thermal resistance. Possible mechanisms of formation of three radical species are suggested, based also on literature data. The kinetics of the disappearance of radical R3 indicated a complex mechanism. Three possible variants were suggested for this mechanism.


1980 ◽  
Vol 45 (3) ◽  
pp. 783-790 ◽  
Author(s):  
Petr Taras ◽  
Milan Pospíšil

Catalytic activity of nickel-molybdenum catalysts for methanation of carbon monoxide and hydrogen was studied by means of differential scanning calorimetry. The activity of NiMoOx systems exceeds that of carrier-free nickel if x < 2, and is conditioned by the oxidation degree of molybdenum, changing in dependence on the composition in the region Mo-MoO2. The activity of the catalysts is adversely affected by irradiation by fast neutrons, dose 28.1 Gy, or by γ rays using doses in the region 0.8-52 kGy. The system is most susceptible to irradiation in the region of low concentrations of the minor component (about 1 mol.%). The dependence of changes in catalytic activity of γ-irradiated samples on the dose exhibits a maximum in the range of 2-5 kGy. The changes in catalytic activity are stimulated by the change of reactivity of the starting mixed oxides, leading to different kinetics of their reduction and modification of their adsorption properties. The irradiation of the catalysts results in lowered concentration of the active centres for the methanation reaction.


1983 ◽  
Vol 48 (11) ◽  
pp. 3202-3208 ◽  
Author(s):  
Zdeněk Musil ◽  
Vladimír Pour

The kinetics of the reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst (8.36 mass % CuO) were determined at temperatures between 413 and 473 K. The reaction was found to be first order in NO and zero order in CO. The observed kinetics are consistent with a rate equation derived from a mechanism proposed on the basis of IR spectroscopic measurements.


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