The reaction of 2-butyne with hydrogen catalyzed by nickel, copper, cobalt, iron, and nickel–copper alloys

1970 ◽  
Vol 48 (13) ◽  
pp. 2075-2089 ◽  
Author(s):  
R. S. Mann ◽  
C. P. Khulbe

The reaction between hydrogen and 2-butyne over unsupported nickel, copper, cobalt, iron, and nickel–copper alloys has been investigated in a static constant volume system between 30 and 250 °C for a wide range of reactant ratios. The reaction over metals and their alloys is simple hydrogenation, the early stages being principally a selective production of cis-2-butene with small yields of polymers. The order of reaction with respect to hydrogen was one and independent of temperature. While the order of reaction over cobalt and copper with respect to 2-butyne was zero, it was slightly negative and temperature dependent for nickel and nickel–copper alloys. The selectivity was independent of initial hydrogen pressure for nickel, cobalt, copper and most of the nickel–copper alloys. The overall activation energy for nickel, cobalt, and copper were 9.1, 6.6, 33.5 kcal/mole, respectively. Selectivity and extent of polymerization increased with increasing amounts of copper in the nickel–copper alloy.

1968 ◽  
Vol 46 (4) ◽  
pp. 623-633 ◽  
Author(s):  
R. S. Mann ◽  
K. C. Khulbe

The reaction between methylacetylene and hydrogen over unsupported nickel, copper, and their alloys has been investigated in a static constant volume system between 20 and 220 °C for a wide range of reactant ratios. The order of reaction with respect to hydrogen was one and nearly independent of temperature. While the order of reaction with respect to methylacetylene over nickel catalyst was slightly negative and temperature dependent, it was always positive and nearly independent of temperature for copper and copper-rich alloys. Selectivity was independent of initial hydrogen pressure for nickel and copper only; for others it decreased rapidly with increasing hydrogen pressure. The overall activation energy varied between 9 and 21.2 kcal/g mole. Selectivity and extent of polymerization increased with increasing amount of copper in the alloy.


The collective electron theory of ferromagnetism is extended to include in the expression for the energy associated with the magnetization a term in the fourth power of the magnetization. A second adjustable parameter, similar to the kθ'/ϵ 0 of the Stoner treatment, is thus introduced. Detailed comparison with experiment of a number of properties of nickel, nickel-cobalt and nickel-copper alloys, is carried out. A high degree of co-ordination of the properties of nickel is obtained by a suitable choice of the two parameters, which are thereby determined within fairly close limits. The temperature variation of electronic specific heat and spontaneous magnetization of nickel is quantitatively covered, as is the magnetocaloric temperature change accompanying changes in external field. The spontaneous magnetization, temperature curves of cubic cobalt and four nickel-copper alloys are similarly covered, and a simple interpretation can be given of the adherence to the law of corresponding states of nickel-cobalt alloys and the deviation therefrom of the nickel-copper alloys. The model accounts qualitatively for the field-magnetization isothermals and for the variation of the magnetocaloric temperature change with magnetization. A detailed examination shows that the differences between theory and observation, where they exist, are due to effects not covered by the collective electron theory. The main discrepancies can be accounted for on the assumption that a small fraction of the volume of the material is made up of groups of atoms of varying size with a Langevin distribution of their magnetic axes. These groups may be called small domains. The problem is complicated by the fact that the field values computed theoretically are critically dependent on the parameters, of which a sufficiently close estimate cannot be made. However, for particular values of both kθ'/ϵ 0 and A a good fit with experiment over a wide temperature range is obtained when it is assumed that the domains are of sizes varying from 10 3 atoms upwards, the largest proportion of domains being of 10 4 to 10 5 atoms, and the volume occupied by such domains probably being much less than 10% of the total volume of material. It is shown that the hitherto unexplained large temperature variation, derived from the experimental results, in the value of —1/ σ (∂ E /∂ σ ) T corresponding to the Weiss molecular field coefficient, is an almost direct consequence of the basic physical premises of the collective electron treatment.


Alloy Digest ◽  
1966 ◽  
Vol 15 (1) ◽  

Abstract MONEL Alloy 402 is a nickel-copper alloy developed for use in the pickling of steel and copper alloys. This datasheet provides information on composition, physical properties, hardness, and tensile properties. It also includes information on corrosion resistance as well as forming, heat treating, machining, joining, and surface treatment. Filing Code: Ni-110. Producer or source: Huntington Alloy Products Division, An INCO Company.


The spontaneous magnetization (σ 0 , T ) of a ferromagnetic may be deduced exclusively from the determination of magnetic isothermals, or in conjunction with magnetocaloric measurements. Values of σ 0, T of a nickel + copper alloy containing 30·75 at. % of copper have been obtained near its Curie temperature using both of these techniques and are shown to be in good agreement. Measurements of spontaneous magnetization and Curie temperature ( θ f ) of nickel + copper alloys containing up to 54·11 at. % of copper using the purely magnetic techniques are described. These measurements were performed over a temperature range from θ f down to 80 °K in all cases, and to 23 °K in the cases of alloys containing over 30 at. % of copper. The magnetic moments per atom ( p B ) of the alloys, which are deduced from the measurements, vary linearly over a wide range of composition, extrapolating to p B = 0 at 53 at. % of copper. This value is in good agreement with that obtained by Meyer & Wolff (1958), and contrary to that based on the familiar measurements of Alder (1916). The reduced magnetization-temperature curves of some of the alloys are given and these show a continuous marked decrease in fullness with increasing copper content.


1968 ◽  
Vol 46 (20) ◽  
pp. 3249-3254 ◽  
Author(s):  
R. S. Mann ◽  
D. E. Tiu

The reaction between allene and hydrogen over unsupported nickel, iron, and cobalt catalysts has been studied in a static constant volume system for a wide range of temperature and reactant ratios. The reaction over metals is largely simple hydrogenation, the early stages being principally a selective formation of propylene with small yields of reduced polymers of allene. The orders of the hydrogenation were 1 and 0 with respect to hydrogen and allene respectively, and were temperature independent. The overall apparent activation energies for nickel, iron, and cobalt were 6.5, 7.6, and 6.9 kcal/mole respectively. Selectivity was highest with nickel, and least with cobalt.


The collective electron treatment of ferromagnetism (Stoner 1938 a , 1939) is applied to the magnetic and thermal properties of nickel and nickel-copper alloys. In § 1 a brief description is given of the theoretical background, together with the necessary extensions of the basic treatment, in particular so as to cover the effects of the overlap of the electronic d and s energy bands. With simplifying assumptions regarding the effect of alloying on the electronic structure, and using a limited range of observational data, estimates are obtained of the variation of the specifying parameters, band width and interchange interaction, for nickel-copper alloys, over a wide range of composition (§ 2). A discussion is given in § 3 of the dependence of the electron distribution on temperature. Calculations are carried out of the variation of the number of holes in the d band, due to the temperature redistribution of electrons between the bands (transfer effect). Other temperature effects, such as the variation of the specifying parameters due to thermal expansion, are briefly discussed, though they are not included in the main treatment (§§ 1 and 4). The treatment is applied to the temperature variation of susceptibility above the Curie point (§4). For nickel-rich alloys satisfactory agreement is obtained with experimental results (figures 10, 11 and 12). For copper-rich alloys the observed high-temperature increase of susceptibility is well explained (figure 13), but no interpretation can be given of the observed low-temperature variation. It is suggested that this may be due to inhomogeneities in composition. A discussion is given in § 5 of the bearing of the treatment on the electronic heat at high temperatures. Comparison is made with the relevant experimental results for nickel above the Curie point. Application is also made to the low-temperature electronic heat of nickel-copper alloys (§5). The general character of the variation of the electronic heat with composition is covered satisfactorily in the nickel-rich regions, but in the copper-rich regions discrepancies occur, similar to those for the low-temperature susceptibility (§4). In §6 a brief account is given of the results of a preliminary analysis of the magnetic properties of nickel alloys other than those with copper.


Alloy Digest ◽  
1983 ◽  
Vol 32 (3) ◽  

Abstract RA 400 is a ductile nickel-copper alloy that is characterized by resistance to a wide range of corrosive environments, freedom from stress-corrosion cracking, and good strength and toughness over a wide temperature range. This alloy is often chosen to handle sulfuric acid under reducing conditions. Its uses include marine components, caustic evaporators and chemical processing equipment. This datasheet provides information on composition, physical properties, hardness, elasticity, and tensile properties as well as creep. It also includes information on corrosion resistance as well as forming, heat treating, machining, and joining. Filing Code: Ni-284. Producer or source: Rolled Alloys Inc..


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