Nickel equilibriums

Bra] Bradley, A.J., Cox, W.F., Goldschmidt, H.J., An X-Ray Study of the Iron-Copper-Nickel Equilibrium Diagram at Various Temperatures , J. Inst. Met., 67, 189-201 (1941) (Crys. Stracture, Experimental, Phase Diagram, Phase Relations, 14)... 

Nayak S K, Khanna S N, Rao B K and Jena P 1997 Physics of nickel clusters energetics and equilibrium geometries J. Phys. Chem. A 101 1072... 

An equilibrium constant for binding of 3.8c to the nickel(II)(L-tryptophan) complex of 805 M has been obtained, compared to 530 M in the presence of glycine... 

Thermodynamically, the formation of methane is favored at low temperatures. The equilibrium constant is 10 at 300 K and is 10 ° at 1000 K (113). High temperatures and catalysts ate needed to achieve appreciable rates of carbon gasification, however. This reaction was studied in the range 820—1020 K, and it was found that nickel catalysts speed the reaction by three to four orders of magnitude (114). The Hterature for the carbon-hydrogen reaction has been surveyed (115). 

Isomerization of sorbitol, D-mannitol, L-iditol, and dulcitol occurs in aqueous solution in the presence of hydrogen under pressure and a nickel—kieselguhr catalyst at 130—190°C (160). In the case of the first three, a quasiequiUbrium composition is obtained regardless of starting material. Equilibrium concentrations are 41.4% sorbitol, 31.5% D-mannitol, 26.5% L-iditol, and 0.6% dulcitol. In the presence of the same catalyst, the isohexides estabUsh an equihbrium at 220—240°C and 15.2 MPa (150 atm) of hydrogen pressure, having the composition 57% isoidide, 36% isosorbide, and 7% isomannide (161). 

Analogously, pyrazolyl-aluminate and -indate ligands have been prepared <75JCS(D)749) and their chelating properties evaluated with cobalt, nickel, copper and zinc. Gallyl derivatives of pyrazoles and indazoles have been extensively studied by Storr and Trotter e.g. 75CJC2944) who determined several X-ray structures of these compounds. These derivatives exist in the solid state as dimers, such as (212) and (288). A NMR study in acetone solution showed the existence of a slow equilibrium between the dimer (212) and two identical tautomers (289) and (290) (Section 4.04.1.5.1) (81JOM(215)157). 

Botli reactions involve the formation of a vapour-uatisporting species from four gaseous reactant molecules, but whereas the tetra-iodide of zirconium is a stable molecule, the nickel teU acarbonyl has a relatively small stability. The equilibrium constatits for these reactions are derived from the following considerations ... 

The kinetics of spinodal decomposition is complicated by the fact that the new phases which are formed must have different molar volumes from one another, and so tire interfacial energy plays a role in the rate of decomposition. Anotlrer important consideration is that the transformation must involve the appearance of concenuation gradients in the alloy, and drerefore the analysis above is incorrect if it is assumed that phase separation occurs to yield equilibrium phases of constant composition. An example of a binary alloy which shows this feature is the gold-nickel system, which begins to decompose below 810°C. 

The analysis of oxidation processes to which diffusion control and interfacial equilibrium applied has been analysed by Wagner (1933) who used the Einstein mobility equation as a starting point. To describe the oxidation for example of nickel to the monoxide NiO, consideration must be given to tire respective fluxes of cations, anions and positive holes. These fluxes must be balanced to preserve local electroneutrality tliroughout the growing oxide. The flux equation for each species includes a term due to a chemical potential gradient plus a term due to the elecuic potential gradient... 

To fully understand the formation of the N13S2 scale under certain gas conditions, a brief description needs to be given on the chemical aspects of the protective (chromium oxide) Ci 203/(nickel oxide) NiO scales that form at elevated temperatures. Under ideal oxidizing conditions, the alloy Waspaloy preferentially forms a protective oxide layer of NiO and Ci 203 The partial pressure of oxygen is such that these scales are thermodynamically stable and a condition of equilibrium is observed between the oxidizing atmosphere and the scale. Even if the scale surface is damaged or removed, the oxidizing condition of the atmosphere would preferentially reform the oxide scales. 

The phase rule is a mathematical expression that describes the behavior of chemical systems in equilibrium. A chemical system is any combination of chemical substances. The substances exist as gas, liquid, or solid phases. The phase rule applies only to systems, called heterogeneous systems, in which two or more distinct phases are in equilibrium. A system cannot contain more than one gas phase, but can contain any number of liquid and solid phases. An alloy of copper and nickel, for example, contains two solid phases. The rule makes possible the simple correlation of very large quantities of physical data and limited prediction of the behavior of chemical systems. It is used particularly in alloy preparation, in chemical engineering, and in geology. 

For alloys containing up to about 27% Ni in Fe, the equilibrium phase at room temperature is bee. However, in the neighborhood of 30% Ni either the fee or bee phases can be obtained at room temperature as the result of various heat treatments. For nickel concentrations greater than 30%, the structure is fee. Hence, the unusually large volumetric phenomena are characteristic of the fee phase. 

Monomer-oligomer equilibria. [Ni(Me-sal)2], mentioned above as a typical planar complex, is a much studied compound. In pyridine it is converted to the octahedral bispyridine adduct (/zsoo = 3.1 BM), while in chloroform or benzene the value of is intermediate but increases with concentration. This is ascribed to an equilibrium between the diamagnetic monomer and a paramagnetic dimer, which must involve a coordination number of the nickel of at least 5 a similar explanation is acceptable also for the paramagnetism of the solid when heated above 180°C. The trimerization of Ni(acac)2 to attain octahedral coordination has already been referred to but it may also be noted that it is reported to be monomeric and planar in dilute chloroform solutions. 

Table 1. Parameters of the interatomic potentials. Distances are given in as, densities in flg, charges in e and energies in Ry. ri4s and Vc have been set to 0.57 and 8.33 ag for iron. The corresponding values for nickel are 0.85 and 8.78 ag ao denotes the equilibrium lattice constant of the elements po is the electron density at equilibrium for the perfect lattices, i.e. 0.002776 ag and 0.003543 ag for iron and nickel respectively.

A promoted nickel type catalyst contained in the reactor tubes is used at temperature and pressure ranges of 700-800°C and 30-50 atmospheres, respectively. The reforming reaction is equilibrium limited. It is favored at high temperatures, low pressures, and a high steam to carbon ratio. These conditions minimize methane slip at the reformer outlet and yield an equilibrium mixture that is rich in hydrogen. ... 

Metals are most active when they first deposit on the catalyst. With time, they lose their initial effectiveness through continuous oxidation-reduction cycles. On average, about one third of the nickel on the equilibrium catalyst will have the activity to promote dehydrogenation reactions. 

It is usually more accurate to back-calculate the feed metals trom the equilibrium catalyst data than to analyze the feed regularly, l nickel will be a regular component of the feed, passivators are available. If nickel affects operation and margins, it is often beneficial to use antimony to passivate the nickel. This can be attractive if the nickel on the equilibrium catalyst is greater than 1,000 ppm. 

Soluble corrosion products may increase corrosion rates in two ways. Firstly, they may increase the conductivity of the electrolyte solution and thereby decrease internal resistance of the corrosion cells. Secondly, they may act hygroscopically to form solutions at humidities at and above that in equilibrium with the saturated solution (Table 2.7). The fogging of nickel in SO2-containing atmospheres, due to the formation of hygroscopic nickel sulphate, exemplifies this type of behaviour. However, whether the corrosion products are soluble or insoluble, protective or non-protective, the... 

The equilibrium of metals with molten sodium hydroxide and with fused alkali chlorides " has been studied in detail. Williams, Grand and Miller studied the reaction of molten sodium hydroxide with nickel. 

Nickel occupies an intermediate position in the electrochemical series Ni2 /Ni = -0-227 V, so that it is more noble than Zn and Fe but less noble than Sn, Pb and Cu. Figure 4.21 shows a revised potential-pH equilibrium (Pourbaix) diagram for the Ni-H O system at 25°C. The existence of the higher anhydrous oxides Nij04, NijO, and NiOj shown in an earlier diagram appears doubtful in aqueous systems in the absence of positive identification of such species. It is seen that ... 

The steel will be considered to be an ideal ternary solution, and therefore at all temperatures a, = 0-18, Ani = 0-08 and flpc = 0-74. Owing to the Y-phase stabilisation of iron by the nickel addition it will be assumed that the steel, at equilibrium, is austenitic at all temperatures, and the thermodynamics of dilute solutions of carbon in y iron only are considered. 

Now to complete the solution of the problem one would need to know the solution laws for iron, and a small amount of nickel, in each of these carbide phases, since equilibrium requires that and a , in the segregated carbide must be 0-74 and 0-08 respectively as well as a., being 0-18. At present nothing is known about these laws except that the metal atoms might well be randomly distributed in the carbide phase, in which case, as an example. 

Not all metals react with aqueous acids. Among the common metals, magnesium, aluminum, iron, and nickel liberate H2 as zinc does. Other metals, including copper, mercury, silver, and gold, do not produce measurable amounts of hydrogen even though we make sure that the equilibrium state has been attained. With these metals, hydrogen is not produced and it is surely not just because of slow reactions. Apparently... 

The same sort of competition for electrons is involved in reaction (11), in which Zn(s) releases electrons and Cu+2 accepts them. This time the competition for electrons is such that equilibrium favors Zn+2 and Cu(s). By way of contrast, compare the reaction of metallic cobalt placed in a nickel sulfate solution. A reaction occurs,... 

This paper surveys the field of methanation from fundamentals through commercial application. Thermodynamic data are used to predict the effects of temperature, pressure, number of equilibrium reaction stages, and feed composition on methane yield. Mechanisms and proposed kinetic equations are reviewed. These equations cannot prove any one mechanism however, they give insight on relative catalyst activity and rate-controlling steps. Derivation of kinetic equations from the temperature profile in an adiabatic flow system is illustrated. Various catalysts and their preparation are discussed. Nickel seems best nickel catalysts apparently have active sites with AF 3 kcal which accounts for observed poisoning by sulfur and steam. Carbon laydown is thermodynamically possible in a methanator, but it can be avoided kinetically by proper catalyst selection. Proposed commercial methanation systems are reviewed. 

The equilibrium ratios of hydrogen-to-hydrogen sulfide for the reaction, derived (34) from available thermodynamic data (35), are plotted in Figure 10 as a function of temperature. When Ph2/Ph2s over the catalyst is less than the equilibrium value, the nickel can be sulfided and hence poisoned. Conversely, when this ratio is greater than the equi-... 

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