Group VIII 8-10 . Iron, Cobalt, Nickel

The most prevalent modification of the disulfide, FeS2, is pyrite, which may be visualized as a distorted NaCl structure where the Fe atoms occupy sodium positions and S2 groups are placed with their centers at the chloride positions. Pyrite is a largely occurring crystal with semiconductor properties Eg = 0.95 eV). Another modification of FeS2 is the very similar to pyrite but somewhat less regular marcasite structure. 

A number of selenium and tellurium compounds of the presently discussed metals show a quite different behavior from the Fe-S system. Iron and selenium form two compounds FeSe with a broad stoichiometry range and FeSe2 with a much narrower composition field. Below 400 the non-stoichiometric Fei xSe exists by creation of iron vacancies and can have compositions lying between FeySes and Fe3Se4. At low temperatures there exist two phases an a (PbO type) and a f) (NiAs type) phase. The crystal sUiicture of the diselenide, FeSe2, is an orthorhombic, C18 (marcasite) type. In the Fe-Te system, the defect NiAs structure is found at a composition close to FeTei.s, as about one-third of the Fe atoms are missing. At compositions around FeTe the behavior is complex, and the f)-phase has the PbO structure (like FeSe) but with additional metal atoms (i.e., FeuTe). 

Cobalt(II) sulfide, CoS cobalt disulfide, C0S2 cobalt(III) sulfide, C02S3 cobalt(II) selenide, CoSe cobalt selenium, CoSc2 (trogtalite) cobalt(II) telluride, CoTe. 

Nickel(II) sulfide, NiS (millerite) nickel(II, III) sulfide, NisSa (polymidite) nickel(III) sulfide, Ni3S2 nickel sulfide, Ni3S2 (heazelwoodite) nickel sulfide, NiS2 (vaesite) nickel selenide, NiSc2 nickel(II) selenide, NiSe nickel telluride, NiTc2 (melonite). 

The platinum group metals form several binary, pseudo-binary, and ternary chalcogenides. The outstanding features of these compounds as related to catalysis and materials science have been widely reported and reviewed [88], 

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One of the characteristic features of the metal-catalysed reaction of acetylene with hydrogen is that, in addition to ethylene and ethane, hydrocarbons containing more than two carbon atoms are frequently observed in appreciable yields. The hydropolymerisation of acetylene over nickel—pumice catalysts was investigated in some detail by Sheridan [169] who found that, between 200 and 250°C, extensive polymerisation to yield predominantly C4 - and C6 -polymers occurred, although small amounts of all polymers up to Cn, where n > 31, were also observed. It was also shown that the polymeric products were aliphatic hydrocarbons, although subsequent studies with nickel—alumina [176] revealed that, whilst the main products were aliphatic hydrocarbons, small amounts of cyclohexene, cyclohexane and aromatic hydrocarbons were also formed. The extent of polymerisation appears to be greater with the first row metals, iron, cobalt, nickel and copper, where up to 60% of the acetylene may polymerise, than with the second and third row noble Group VIII metals. With alumina-supported noble metals, the polymerisation prod-... 

Cobalt. The speciation of radiocobalt has been selected for discussion in this chapter because it exemplifies an element for which much information already exists regarding its stable chemical speciation, yet there are additional species which have become environmentally important as a result of the activities of the nuclear industry Cobalt, the middle member of the first triad of group VIII transition metals in the Periodic Table (iron, cobalt, nickel), is most stable in the divalent state when in simple compounds. Studies of radionuclide releases from nuclear power plants under tropical conditions in India seem to indicate that... 

The inclusion of iron, cobalt, nickel, and certain other metals in Group VIII.4 enables the alkali-metals lithium, sodium, potassium, rubidium, and caesium to be placed in their natural position as a subgroup of Group I. of the periodic system, in juxtaposition to the related sub-group containing copper, silver, and gold (p. 3). This arrangement... 

The metal catalysts active for steam reforming of methane are the group VIII metals, usually nickel. Although other group VIII metals are active, they have drawbacks for example, iron rapidly oxidizes, cobalt cannot withstand the partial pressures of steam, and the precious metals (rhodium, ruthenium, platinum, and palladium) are too expensive for commercial operation. Rhodium and ruthenium are ten times more active than nickel, platinum, and palladium. However, the selectivity of platinum and palladium are better than rhodium [1]. The supports for most industrial catalysts are based on ceramic oxides or oxides stabilized by hydraulic cement. The commonly-used ceramic supports include a-alumina, magnesia, calcium-aluminate, or magnesium-alu-minate [4,8]. Supports used for low temperature reforming (< 770 K) are... 

In order to produce methanol the catalyst should only dissociate the hydrogen but leave the carbon monoxide intact. Metals such as copper (in practice promoted with ZnO) and palladium as well as several alloys based on noble group VIII metals fulfill these requirements. Iron, cobalt, nickel, and ruthenium, on the other hand, are active for the production of hydrocarbons, because in contrast to copper, these metals easily dissociate CO. Nickel is a selective catalyst for methane formation. Carbidic carbon formed on the surface of the catalyst is hydrogenated to methane. The oxygen atoms from dissociated CO react with CO to CO2 or with H-atoms to water. The conversion of CO and H2 to higher hydrocarbons (on Fe, Co, and Ru) is called the Fischer-Tropsch reaction. The Fischer-Tropsch process provides a way to produce liquid fuels from coal or natural gas. 

This section deals with the ternary compounds formed by rare earth elements and chalcogenides with the elements of groups VI through VIII chromium, manganese, iron, cobalt, nickel and molybdenum. 

Hydrogenation Catalysts. The key to catalytic hydrogenation is the catalyst, which promotes a reaction which otherwise would occur too slowly to be useful. Catalysts for the hydrogenation of nitro compounds and nitriles are generally based on one or more of the group VIII metals. The metals most commonly used are cobalt, nickel, palladium, platinum, rhodium, and mthenium, but others, including copper (16), iron (17), and tellurium... 

Catalysts. The methanation of CO and C02 is catalyzed by metals of Group VIII, by molybdenum (Group VI), and by silver (Group I). These catalysts were identified by Fischer, Tropsch, and Dilthey (18) who studied the methanation properties of various metals at temperatures up to 800°C. They found that methanation activity varied with the metal as follows ruthenium > iridium > rhodium > nickel > cobalt > osmium > platinum > iron > molybdenum > palladium > silver. 

The first reported work on the kinetics of hydrogenolysis reactions of simple hydrocarbons appears to be that of Taylor and associates at Princeton (2-4, 14, 15), primarily on the hydrogenolysis of ethane to methane. The studies were conducted on nickel, cobalt, and iron catalysts. More recently, extensive studies on ethane hydrogenolysis kinetics have been conducted on all the group VIII metals and on certain other metals as well (16,28-83). 

In the hydrogenolysis of the higher alkanes on the nonnoble group VIII metals (i.e., iron, cobalt, and nickel), the mode of cracking is very different from that observed on the noble metals of group VIII (49, 50). On nickel,... 

The successive demethylation scheme of hydrogenolysis just discussed for iron, cobalt, and nickel clearly does not apply to the noble metals of group VIII. This can be seen by examining the product distribution data in Table IV. The amounts of methane observed are much lower than would be expected if the hydrogenolysis occurred by successive demethylation steps. Thus, we have another indication that the noble and nonnoble metals of group VIII behave as two separate classes with regard to their catalytic properties in the hydrogenolysis of hydrocarbons. 

Although iron, cobalt, and nickel occur in the same triad in Group VIII., the three elements differ considerably in their ability to form addition compounds with ammonia. Iron forms few ammino-salts, most of which are unstable, and its tendency to complex-salt formation of the ammine type appears in the complex cyanides and not in the ammines themselves. 

We place hydrogen as the first element in the first period, along with helium. When helium was discovered, Mendeleev put it in the second period. We put the triads of iron, cobalt, and nickel ruthenium, rhodium and palladium and osmium, iridium, and platinum in group VIIIB, in the middle of the table. Mendeleev put them in group VIII. We also have two long groups, the lanthanides and actinides, that were a headache for Mendeleev. 

In Group VIII, each position instead of being filled by a single element is occupied by a group of three elements. Thus there appear in triads iron, cobalt, and nickel ruthenium, rhodium, and palladium and osmium, iridium, and platinum. In this group there is no subdivision into families, but all the members are heavy metals. 

Carbon monoxide has been found to be surprisingly reactive toward the metals in Group VIII, in both their oxidized and unoxidized states. A sizable number of compounds exist in which one or more CO molecules are attached to a metal atom through the carbon typical of these are nickel tetracarbonyl, Ni(CO)4, iron pentacarbonyl, Fe(CO) cobalt carbonyl hydride, Co(CO)4H platinum carbonyl chloride, Pt(CO)2Cl2 and more complicated molecules such as Co4(CO)i2. 

There are nine metals in Group VIII. Only the three in the first eighteen-membered period, iron (Z = 26), cobalt (Z = 27), and nickel (Z = 28) will be treated here. 

It is to be emphasized that this is a text, not a reference book. A number of the less common elements which sometimes find their way into inorganic textbooks are given only slighting treatment. Thus, the Group VIII transition metals, other than iron, cobalt, and nickel, are not discussed and the lanthanides and actinides are mentioned only in passing. I believe that there is enough good chemistry in the remainder of the... 

Imaizumi et al. studied the hydrogenation of l,4-dialkyl-l,3-cyclohexadienes over the nine group VIII (groups 8-10) metals and copper in ethanol at room temperature and atmospheric pressure.122 The selectivity for monoenes formation at 50% conversion increased in the order Os-C, Ir-C < Ru-C, Rh-C, Pt < Pd-C, Raney Fe, Raney Co, Raney Ni, Raney Cu (= 100%). The selectivity for 1,4-addition product increased in the order Os-C, Ir-C < Ru-C, Rh-C, Raney Cu, Raney Fe, Raney Ni < Raney Co, Pd-C, Pt. Extensive formation of 1,4-dialkylbenzenes (more than 50% with the 1,3-dimethyl derivative) was observed over Raney Ni and Pd-C, while they were not formed over Raney Cu, Os-C, and Ir-C. In the hydrogenation of 4-methyl-1,3-pen -tadiene (39) (Scheme 3.15) over group VIII metals in cyclohexane at room temperature and atmospheric pressure, high selectivity to monoenes was obtained with iron, nickel, cobalt, and palladium catalysts where the amounts of the saturate 2-methylpen-... 

Cobalt, in its properties, is an excellent intermediary between iron and nickel, and, moreover, it is clearly a suitable element to constitute the first of the central vertical triads of Group VIII, namely, Co, Eh, and Ir. Hence, if the Periodic Law holds absolutely, the atomic weight of cobalt should exceed that of iron, but not that of nickel. Either, therefore, the atomic weight of cobalt is slightly too high or that of nickel is slightly too low. 

Iron, cobalt, and nickel, with atomic numbers 26, 27, and 28, lie in the center of the first long period, and are described, with their congeners, the platinum metals, as group VIII of the periodic table. They show a. trend in their chemical properties, forming a transition from the metals chromium and manganese, which may assume several oxidation states, and whose higher oxides are acidic, to the more basic and less chemically versatile metals copper and zinc. 

Likewise, the designation of groups as A or B is purely arbitrary. Assignment of ail of the transition metals to B groups has an internal consistency as well as historical precedent.20 Unfortunately, some periodic charts have used A and B in an almost opposite sense.21 In addition, as a historical carryover from the older short form chart, the iron, cobalt, and nickel families were lumped under the nondescript VIII . This stale of confusion led the IUPAC to recommend that the groups... 

Physical and Chemical Properties Iron (Fe) belongs to Group VIII, Period 4, of the Periodic Table of the elements, and its physico-chemical properties are closely related to those of cobalt and nickel. Iron is a sUverish, malleable metal (atomic number 26, atomic mass 55.85, density... 

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