Hydrogen solid solution

Figure 1. Ideal pressure-composition isotherms showing the hydrogen solid-solution phase, a, and the hydride phase, j3. The plateau marks the region of coexistence of the a and fl phases. As the temperature is increased the plateau narrows and eventually disappears at some consolule temperature...

Irodova A.V. (1980) Directional order (k=0) in hydrogen solid solution based on Cubic (C15) Laves phases. (Preprint IAE-3308/9), Moscow, 16. 

Figure 2 SEM (left) and REELM (right) micrographs of a hydrogenated scandium sample. Only the REELM image correctly identifies the scandium solid solution phase (bright) in the presence of the scandium dihydride phase (black).

A new, low-pressure, plasma-assisted proeess for synthesising diamonds has been found by Roy et al [83,84]. An intimate mixture of various forms of carbon with one of many metals (e.g., Au, Ag, Fe, Cu, Ni) is exposed to a microwave plasma derived from pure hydrogen at temperatures ranging from 600-1000 °C. Roy et al postulate a mechanism in which a solid solution of atomic hydrogen and the metal. Me, facilitates dissolution of carbon to form molten droplets of Me -Cj,-H. Diamonds nucleate at the surface of the droplets as the temperature is reduced. 

When addition is complete the mixture is heated under reflux during 5 hours and then the acetone is removed by distillation. The residue is dissolved in water, acidified with hydrochloric acid and the mixture extracted with chloroform. The chloroform extract is stirred with sodium hydrogen carbonate solution and the aqueous layer is separated. The alkaline extract is acidified with hydrochloric acid and filtered. The solid product is drained free from oil on a filter pump, then washed with petroleum ether (BP 40° to 60°C), and dried at 50°C. The solid residue, MP 114° to 116°C, may be crystallized from methanol (with the addition of charcoal) to give p-chlorophenoxyisobutyric acid, MP 118° to 119°C. 

A number of metals have the ability to absorb hydrogen, which may be taken into solid solution or form a metallic hydride, and this absorption can provide an alternative reaction path to the desorption of H,. as gas. In the case of iron and iron alloys, both hydrogen adsorption and absorption occur simultaneously, and the latter thus gives rise to another equilibrium involving the transfer of H,<,s across the interface to form interstitial H atoms just beneath the surface ... 

There are a number of differences between interstitial and substitutional solid solutions, one of the most important of which is the mechanism by which diffusion occurs. In substitutional solid solutions diffusion occurs by the vacancy mechanism already discussed. Since the vacancy concentration and the frequency of vacancy jumps are very low at ambient temperatures, diffusion in substitutional solid solutions is usually negligible at room temperature and only becomes appreciable at temperatures above about 0.5T where is the melting point of the solvent metal (K). In interstitial solid solutions, however, diffusion of the solute atoms occurs by jumps between adjacent interstitial positions. This is a much lower energy process which does not involve vacancies and it therefore occurs at much lower temperatures. Thus hydrogen is mobile in steel at room temperature, while carbon diffuses quite rapidly in steel at temperatures above about 370 K. 

But in metals it is relatively common for solid solutions to form. The atoms of one element may enter the crystal of another element if their atoms are of similar size. Gold and copper form such solid solutions. The gold atoms can replace copper atoms in the copper crystal and, in the same way, copper atoms can replace gold atoms in the gold crystal. Such solid solutions are called alloys. Some solid metals dissolve hydrogen or carbon atoms—steel is iron containing a small amount of dissolved carbon. 

It is essentially a phase diagram which consists of a family of isotherms that relate the equilibrium pressure of hydrogen to the H content of the metal. Initially the isotherm ascends steeply as hydrogen dissolves in the metal to form a solid solution, which by convention is designated as the a phase. At low concentrations the behaviour is ideal and the isotherm obeys Sievert s Law, i.e.,... 

In addition to the surface physics and chemistry phenomena involved, a further effect may follow the interaction at the hydrogen-metal surface, that is the absorption of hydrogen by the bulk phase of the metal. This absorption leads to the formation of a solid solution within a certain, usually low, range of hydrogen concentrations. However, with several transition metals, exceeding a certain limit of hydrogen concentration results in the formation of a specific crystallographically distinct phase of the... 

This review aims to present an account of the catalytic properties of palladium and nickel hydrides as compared with the metals themselves (or their a-phase solid solutions with hydrogen). The palladium or nickel alloys with the group lb metals, known to form /8-phase hydrides, will be included. Any attempts at commenting on the conclusions derived from experimental work by invoking the electronic structure of the systems studied will of necessity be limited by our as yet inadequate knowledge concerning the electronic structure of the singular alloys, which the hydrides undoubtedly are. 

As has been shown by the X-ray diffraction method the parent metals (i.e. Pd or Ni), the a-phase, and /3-phase all have the same type of crystal lattice, namely face centered cubic of the NaCl type. However, the /9-phase exhibits a significant expansion of the lattice in comparison with the metal itself. Extensive X-ray structural studies of the Pd-H system have been carried out by Owen and Williams (14), and on the Ni-H system by Janko (8), Majchrzak (15), and Janko and Pielaszek (16). The relevant details arc to be found in the references cited. It should be emphasized here, however, that at moderate temperatures palladium and nickel hydrides have lattices of the NaCl type with parameters respectively 3.6% and 6% larger than those of the parent metals. Within the limits of the solid solution the metal lattice expands also with increased hydrogen concentration, but the lattice parameter does not depart significantly from that of the pure metal (for palladium at least up to about 100°C). 

Neutron diffraction studies have shown that in both systems Pd-H (17) and Ni-H (18) the hydrogen atoms during the process of hydride phase formation occupy octahedral positions inside the metal lattice. It is a process of ordering of the dissolved hydrogen in the a-solid solution leading to a hydride precipitation. In common with all other transition metal hydrides these also are of nonstoichiometric composition. As the respective atomic ratios of the components amount to approximately H/Me = 0.6, the hydrogen atoms thus occupy only some of the crystallographic positions available to them. 

Strictly a-solid solution of hydrogen in a metal catalyst studied. 

It is found in this way that crystalline hydrogen at temperatures somewhat below the melting point is a nearly perfect solid solution of symmetric and antisymmetric molecules, the latter retaining the quantum weight 3 for the state with j = 1 as well as the spin quantum weight 3. This leads to the expression... 

The possibility of the expression of the entropy of hydrogen as the sum of these terms was first noted by Giauque, who observed that it indicated the formation of nearly ideal solid solutions between symmetrical and antisymmetrical hydrogen and the retention of the quantum weight 9 for the latter. 

Suspensions of semiconductors with heterojunctions formed by CdS or solid solution ZnyCdi-yS and Cu , S have been prepared and tested as photocatalysts for photochemical hydrogen production [278]. With platinized powders of Zno.nCdo.ssS/CujS in solution containing both S and SOj ions, hydrogen was generated concomitantly with thiosulfate ions with quantum yield of about 0.5. 

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