Mercury structure

One of the important electrochemical interfaces is that between water and liquid mercury. The potential energy functions for modeling liquid metals are, in general, more complex than those suitable for modeling sohds or simple molecular liquids, because the electronic structure of the metal plays an important role in the determination of its structure." However, based on the X-ray structure of liquid mercury, which shows a similarity with the solid a-mercury structure, Heinzinger and co-workers presented a water/Hg potential that is similar in form to the water/Pt potential described earlier. This potential was based on quantum mechanical calculations of the adsorption of a water molecule on a cluster of mercury atoms. ... 

Three linear organogermanium mercury structures have been reported (116, 117, 164). The two independent molecules in the asymmetric unit of [(C6H5)3Ge]2Hg differ in that one is centrosymmetric at mercury while the other has a Ge—Hg—Ge angle of 178.68°, with a shortening of the contiguous Ge—Hg bond from 2.543 to 2.514 A (164). 

A kinetic study of the reaction was also performed in which NMR-obtained rate data were correlated with mercurial structure changes (12). This study revealed a quite distinct reactivity order which, coupled with a 1 1 reactant stoichiometry, indicates a 1,3-dipolar electrophilic attack by ozone via a SE2 or four-center process. Although the exact mechanism was not conclusively proved, it is certain that neither the SE1 or SEi processes were operative during these reactions. 

In Fig. III-7 we show a molecular dynamics computation for the density profile and pressure difference P - p across the interface of an argonlike system [66] (see also Refs. 67, 68 and citations therein). Similar calculations have been made of 5 in Eq. III-20 [69, 70]. Monte Carlo calculations of the density profile of the vapor-liquid interface of magnesium how stratification penetrating about three atomic diameters into the liquid [71]. Experimental measurement of the transverse structure of the vapor-liquid interface of mercury and gallium showed structures that were indistinguishable from that of the bulk fluids [72, 73]. 

There is a fair amount of work reported with films at the mercury-air interface. Rice and co-workers [107] used grazing incidence x-ray diffraction to determine that a crystalline stearic acid monolayer induces order in the Hg substrate. Quinone derivatives spread at the mercury-n-hexane interface form crystalline structures governed primarily by hydrogen bonding interactions [108]. 

The electrode potential of aluminium would lead us to expect attack by water. The inertness to water is due to the formation of an unreactive layer of oxide on the metal surface. In the presence of mercury, aluminium readily forms an amalgam (destroying the original surface) which is. therefore, rapidly attacked by water. Since mercury can be readily displaced from its soluble salts by aluminium, contact with such salts must be avoided if rapid corrosion and weakening of aluminium structures is to be prevented. 

The pressures involved in porosimetry are so high (e.g. 1000 atm = 6-6 ton in" ) that the question as to whether the pore structure is damaged by mercury intrusion naturally arises. This possibility was recognized by Drake, but as a result of several intrusion-extrusion runs at pressures up to 4000 atm on a number of porous catalysts Drake concluded that any deformation caused by compression was elastic and therefore not permanent. 

In Unger and Fischer s study of the effect of mercury intrusion on structure, three samples of porous silica were specially prepared from spherical particles 100-200 pm in diameter so as to provide a wide range of porosity (Table 3.16). The initial pore volume n (EtOH) was determined by ethanol titration (see next paragraph). The pore volume u (Hg, i) obtained from the first penetration of mercury agreed moderately well with u fEtOH),... 

A typical example, from the extensive study by Kamakin on an alumina-silica gel, is shown in Fig. 3.32. When the mercury pressure was reduced to 1 atm at the end of the first cycle, 27 per cent of the intruded mercury was retained by the sample a second intrusion run followed a different path from the first, whereas the second extrusion curve agreed closely with the first. Change in f re structure of the kind described above could perhaps account for the difference between the two intrusion curves, but could not explain the reproducibility of the remainder of the loop. There is no doubt that hysteresis can exist in the absence of structural change. 

Despite these various limitations, mercury pwrosimetry constitutes an indispensable tool for the quantitative study of pore structure, but it needs to be supplemented by other techniques, if a reliable picture of the pore system is to be built up. 

Again, as with pyridopyrimidines, the main reaction is oxidation of di- or poly-hydro derivatives to fully aromatic structures, often merely by air or oxygen. In some cases the reagent of choice is mercury(II) oxide, whilst other reagents used include sulfur, bromine, chloranil, chromium trioxide-acetic acid, hydrogen peroxide, and potassium ferricyanide, which also caused oxidative removal of a benzyl group in the transformation (306) (307)... 

Dimethylpyrazole (L) reacts with mercury(II) chloride to give complexes of the structure L2(HgCl2)3. In connection with metallotropy (Section 4.04.1.5.1) the behaviour of compounds (295) has been described. These phenylmercury derivatives were synthesized by the action of phenylmercury hydroxide on the appropriate pyrazole (71MI40400). 

The possible structures for isothiazoles are discussed in Section 4.01.1, and attention in this chapter will be directed mainly towards the aromatic systems, as defined in Section 4.01.1. The saturated isothiazole 1,1-dioxides (5) are known as sultams, and bicyclic compounds of structure (6) are called isopenems. Isothiazoles readily coordinate to metals (76MI41703, 78MI41701, 79MI41700, 80MI41701). Coordination usually takes place through the nitrogen atom, but sulfur coordination can occur with soft metals such as cadmium or mercury. Some specific coordination complexes are discussed in later sections. 

Liquid-Metal Corrosion Liquid metals can also cause corrosion failures. The most damaging are liqmd metals which penetrate the metal along grain boundaries to cause catastrophic failure. Examples include mercury attack on aluminum alloys and attack of stainless steels by molten zinc or aluminum. A fairly common problem occurs when galvanized-structural-steel attachments are welded to stainless piping or eqmpment. In such cases it is mandatoty to remove the galvanizing completely from the area which will be heated above 260°C (500°F). 

MIR), requires the introduction of new x-ray scatterers into the unit cell of the crystal. These additions should be heavy atoms (so that they make a significant contribution to the diffraction pattern) there should not be too many of them (so that their positions can be located) and they should not change the structure of the molecule or of the crystal cell—in other words, the crystals should be isomorphous. In practice, isomorphous replacement is usually done by diffusing different heavy-metal complexes into the channels of preformed protein crystals. With luck the protein molecules expose side chains in these solvent channels, such as SH groups, that are able to bind heavy metals. It is also possible to replace endogenous light metals in metal-loproteins with heavier ones, e.g., zinc by mercury or calcium by samarium. 

Before 1950, it was impossible to examine the true structure of a solid surface, because, even if a surface is cleaned by flash-heating, the atmospheric molecules which constantly bombard a solid surface very quickly re-form an adsorbed monolayer, which is likely to alter the underlying structure. Assuming that all incident molecules of oxygen or nitrogen stick to the surface, a monolayer will be formed in 3 x 10 second at 1 Torr (=1 mm of mercury), that is, at 10 atmosphere a monolayer forms in 3 s at 10 Torr, or 10 atmosphere but a complete monolayer takes about an hour to form at 10 Torr. The problem was that in 1950, a vacuum of 10" Torr was not achievable lO Torr was the limit, and that only provided a few minutes grace before an experimental surface became wholly contaminated. 

Structure and dynamics of water on Pt(lOO) [46,47,127-129], Pt(lll) [62,129,130], and the rigid [131] and liquid [132,133] mercury surface have been investigated. This subject has also been reviewed recently [134]. As an example, I want to briefly discuss the results on the water/mercury interface. 

Fig. 5 shows data from a simulation of TIP4P water that is confined on both sides by a rhombohedral mercury crystal with (111) surface structure. Bosio et al. [135] deduce from their X-ray studies that a solid o-mercury lattice with a larger lattice constant in the z direction may be used as a good structural model for liquid mercury. Thus, the mercury phase was modeled as a rigid crystal in order to simplify the simulations. The surface of such a crystal shows rather low corrugation. 

Pc- (c) Dipole density p. (d) Water contribution to the surface potential x calculated from the charge density Pc by means of Eq. (1). All data are taken from a 150 ps simulation of 252 water molecules between two mercury phases with (111) surface structure using Ewald summation in two dimensions for the long-range interactions. 

The major difference of the water structure between the liquid/solid and the liquid/liquid interface is due to the roughness of the liquid mercury surface. The features of the water density profiles at the liquid/liquid interface are washed out considerably relative to those at the liquid/solid interface [131,132]. The differences between the liquid/solid and the liquid/liquid interface can be accounted for almost quantitatively by convoluting the water density profile from the Uquid/solid simulation with the width of the surface layer of the mercury density distribution from the liquid/liquid simulation [66]. 

Porosity and surface area are routinely measured by nitrogen absorption-desorption, mercury intrusion, and low-angle X ray. The electron microscope (EM) provides direct visual evidence of pore size and pore-size distribution. Thus, a combination of EM and conventional methods of pore-size measurement should provide reliable information on the pore structure of polymers. 

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