Mixed metal systems condensed

Noteworthy features of this method are that nonhydrated oxides without residual hydroxo groups are obtained, due to the aprotic conditions, and that in bimetallic systems the metals M and M have an alternate order (no phase separation), due to the reaction mechanism (Eq. (1.7)). A limitation of nonhydrolytic processes is that the M/M ratio is not freely selectable if fully condensed products are targeted. Eor this reason, sol-gel processes of mixed metal systems are sometimes initiated by nonhydrolytic reactions (to obtain a high homogeneity) and then completed by hydrolytic reactions (to obtain complete hydrolysis and condensation). 

There are several interesting families of inorganic mixed-valence compounds that we have not discussed here (see Yvon, 1979 McCarley, 1982). For example, there are metal-cluster compounds such as the Chevrel phases, M,jMo6X8(X = S or Se) and condensed metal-cluster chain compounds such as TlMojScj, TijTe, NaMo O and M PtjO. TTF halides and TTF-TCNQ complexes (Section 1.9) constitute molecular mixed-valent systems in which the mixed valency is associated with an entire molecule the charge on TTF in such compounds is nonintegral. The structure of TTF-Br(, 79 and... 

To improve process economics, further work is needed to improve catalyst lifetimes. A more stable system employed a noble metal-loaded potassium L-zeolite catalyst for the condensation of ethanol with methanol to produce a 1-propanol and 2-methyl-l-propanol (US patent no. 5,300,695) (18). However, yields were small compared with the large amounts of CO and C02 produced from the methanol. More recently, Exxon patented a noble metal-loaded alkali metal-doped mixed metal (Zr, Mn, Zn) oxide (US patent nos. 6,034,141 and 5,811,602) (19,20). The catalyst was used in a syngas atmosphere. As with other catalysts, the higher temperatures resulted in decomposition of methanol. Changes in catalyst composition were noted at higher temperatures, but the stability of the catalyst was not discussed. Recently, compositions including Ni, Rh, Ru, and Cu were investigated (21,22). 

Mixed metal alkoxide systems are also of interest as a means of creating additional hybrid systems. However, recognition of the large differences in their hydrolysis and condensation rates is crucial. For example, if titanium isopropoxide is made to react under the same conditions as might be used for TEOS, hydrolysis and condensation rapidly occur and lead to particulate rather than network formation of Ti02- Cocondensation with TEOS under these conditions does not occur because of the fast precipitation of the titanium dioxide species. Indeed, of the general metal alkoxides, those based on silicon tend to be more easily controlled because of their slower hydrolysis... 

Polyphosphate is defined in this work as any linear, condensed phosphate, in which the phosphate, but not necessarily the system containing the phosphate exhibits the conditions 1 < M2O/P2O5 < 2, where M is any single or mixed metals with a total equivalency of unity. The definition is required to differentiate the total composition of a system from the polyphosphates crystallizing in a melt. An example is a polyphosphate crystallizing from a melt of ultraphosphate composition where several metal oxides may be involved. 

The chemistry of both Ru-W and Os-W mixed-metal clusters was extensively investigated by Chi et al., and a number of exciting discoveries were made. These include the reversible scission of a coordinated acetylide ligand on the acetylide cluster 168, which can be prepared from the condensation of CpW(CO)3(C2Ph) and Ru3(GO)i2 in refluxing toluene.The carbide clusters 169 and 170 were formed when 168 was heated with Ru3(CO)i2 in heptane. Interestingly, the reaction sequence can be reversed to regenerate the acetylide cluster 168 in the presence of pressurized CO. This kind of reactivity is seldom observed for semi-encapsulated ruthenium carbide systems. 

Metafile arsenic can be obtained by the direct smelting of the minerals arsenopyrite or loeUingite. The arsenic vapor is sublimed when these minerals are heated to about 650—700°C in the absence of air. The metal can also be prepared commercially by the reduction of arsenic trioxide with charcoal. The oxide and charcoal are mixed and placed into a horizontal steel retort jacketed with fire-brick which is then gas-fired. The reduced arsenic vapor is collected in a water-cooled condenser (5). In a process used by Bofiden Aktiebolag (6), the steel retort, heated to 700—800°C in an electric furnace, is equipped with a demountable air-cooled condenser. The off-gases are cleaned in a sembber system. The yield of metallic arsenic from the reduction of arsenic trioxide with carbon and carbon monoxide has been studied (7) and a process has been patented describing the gaseous reduction of arsenic trioxide to metal (8). 

The metal-vapor synthesis, involving co-condensation of nickel vapors, r-BuC = P, and 1,2,4-triphospholyl system leads to the mixed-ligand species 178 (94AGE2330). 

Because systems are normally not designed for use with this type of fluid, certain aspects should be reviewed with the equipment and fluid suppliers before a decision to use such fluids can be taken. These are compatibility with filters, seals, gaskets, hoses, paints and any non-ferrous metals used in the equipment. Condensation corrosion effect on ferrous metals, fluid-mixing equipment needed, control of microbial infection together with overall maintaining and control of fluid dilution and the disposal of waste fluid must also be considered. Provided such attention is paid to these designs and operating features, the cost reductions have proved very beneficial to the overall plant cost effectiveness. 

Mixed clusters NH3/H20 (139-141), NH3/MeOH (61), and NH3/Me2CO (142) have been reacted with bare metal ions and in general the transition metal ions preferred coordination to ammonia whereas the non-transition metal ions such as Mg+ and Al+ were nonselective, showing some similarity to condensed-phase systems. 

In practice, a mixture of actinide dioxide and graphite powder is first pelletized and then heated to 2275 K in vacuum in a graphite crucible until a drop in the system pressure indicates the end of CO evolution. The resulting actinide carbide is then mixed with tantalum powder, and the mixture is pressed into pellets. The reduction occurs in a tantalum crucible under vacuum. At the reduction temperature, the actinide metal is vaporized and deposited on a tantalum or water-cooled copper condenser. 

---