Oxides dioxide . sesquioxide

The relative stabilities of the dioxides, sesquioxides and monoxides for first period transition metals are given in Figure 7.11(c). The stability of the higher oxidation state oxides decreases across the period. As we will discuss later, higher oxidation states can be stabilized in a ternary oxide if the second metal is a basic oxide like an alkaline earth metal. The lines in Figure 7.11(c) can in such cases be used to estimate enthalpies of formation for unstable oxidation states in order to determine the enthalpy stabilization in the acid-base reactions see below. Finally, it should be noted that the relative stability of the oxides in the higher oxidation states increases from the 3d via 4d to the 5d elements, as illustrated for the Cr, Mo and W oxides in Figure 7.11(d). 

Thiophene 1,1-dioxides, sesquioxides, and 1-oxides, general review ... 

FIGURE 21 Oxidation energies, Eq, in Eq. (40), for the lanthanides Ce to Ho. The filled circle is for the cubic C-type sesquioxide and the open circle for the A-type hexagonal structure of the sesquioxide. Negative values indicate that the dioxide is stable. The chemical potential of free O is taken as ixo = 6.12 eV. The solid line just below 1.5 eV indicates the dioxide/sesquioxide... 

Cerium Oxide. The most stable oxide of cerium is cerium dioxide [1306-38-3] Ce02, also called ceria or ceric oxide. When cerium salts are calcined in air or if oxygen is present, this tetravalent Ce(IV) oxide is formed, cerium sesquioxide [1345-13-7] can be prepared in strongly reducing... 

Ln203 are all well eharaeterized. With three exeeptions they are the final produets of eombustion of the metals or ignition of the hydroxides, earbonate, nitrate, ete. The exeeptions are Ce, Pr and Tb, the most oxidized produets of whieh are the dioxides, from whieh the sesquioxides ean be obtained by eontrolled reduetion with H2. Ln203 adopt three strueture types eonventionally elassified as )... 

Melles and Backer " found, from a study of the oxidation of substituted thiophenes with perbenzoic or peracetic acid, that sulfones could be obtained from polysubstituted methyl- and phenyl-thiophenes and that the presence of electron-attracting groups, such as nitro, hindered the oxidation. Oxidation of thiophene - led to a product which was formed through a Diels-Alder reaction between the intermediate thiophene sulfoxide (211) and thiophene sulfone (212) and for which two alternative structures, (213) or (214), were suggested. Similar sesquioxides were also obtained from 2- and 3-methylthiophene and 3-phenylthiophene. The structures were not proved. Bailey and Cummins synthesized thiophene-1,1-dioxide... 

Vanadium forms numerous oxides, the most important of which are vanadium monoxide, vanadium sesquioxide, vanadium dioxide and vanadium pentoxide. In the earlier examples (e.g., oxides of chromium and of niobium) the enthalpy values for the aluminothermic reduction of each of the oxides was given for the purpose of illustration. Normally, the consideration can be restricted to only those oxides which are readily obtained and which can be handled freely without any special or cumbersome precautions. In the case of vanadium for example, it is sufficient to consider the reduction of the sesquioxide (V203) and the pentoxide (V2Os). The pertinent reactions are ... 

Oxidation of thiophene and its derivatives was studied using hydrogen peroxide (H2O2), t-butyl-hydroperoxide and Ti-Beta redox molecular sieve as selective oxidation catalysts. A new reaction pathway was discovered and investigated using C-13 NMR, GC, GC-MS, HPLC, ion chromatography, and XANES. The thiophene oxidized to thiophene-sesquioxide [3a,4,7,7a-tetrahydro-4,7-epithiobenzo[b]-thiophene 1,1.8-trioxide] and the sesquioxide oxidized mostly to sulfate. 2-Methyl-thiophene and 2,5 dimethylthiophene also oxidized to sulfate and sulfone products. The Benzothiophene oxidation product was sulfone. This proposed new reaction pathway is different from prior literature, which reported the formation of thiophene 1,1-dioxide (sulfone ) as a stable oxidation product... 

The chemical properties of berkehum are rare earth-like character because of its half-filled 5/ subsheU and should be simdar to cerium. The element readily oxidizes to berkelium dioxide, Bk02 when heated to elevated temperatures (500°C). In aqueous solutions, the most common oxidation state is -i-3 which may undergo further oxidation to +4 state. A few compounds have been synthesized, the structures of which have been determined by x-ray diffraction methods. These include the dioxide, Bk02 sesquioxide, Bk203 fluoride,... 

The XPS valence band spectra for the dioxides of the transuranium elements (from Np to Bk) have been presented in an extensive and pioneering work that also includes core level spectra and has been for a long time the only photoemission study on highly radioactive compounds. High resolution XPS spectra (AE = 0.55 eV) were recorded on oxidized thin metal films (30 A) deposited on platinum substrates with an isotope separator. (The oxide films for Pu and the heavier actinides may contain some oxides with lower stoichiometry, since starting with Pu, the sesquioxides of the heavier actinides begin to form in high vacuum conditions.)... 

The affinity of selenium for oxygen is less than that of sulphur. The dioxide, SeQ2, is well defined. The trioxide, Se03, is much less stable than its sulphur analogue, and until recently all attempts to isolate it have been unsuccessful (see p. 331). Selenium sesquioxide, Se203, has not been definitely isolated.1 An oxide of composition Se304 has been described,2 but its existence needs confirmation. The existence of a lower oxide, SeO, postulated to explain the characteristic odour of selenium when vaporised in air, is improbable.3... 

The dioxide. PbiO. has rutile structure, and the compound is a strong oxidizing agent. It is also amphiprotic. giving unstable lcad(IV) salts with acids, and orthoplnmbates. M PbOa, or metuplumbates. M PbO.. upon fusion with alkalies. Lead dioxide dissolves in aqueous alkali with formation of the ion Pb(OH)6. the alkali salts of which are isomorphous with the corresponding stannates and platinates. Lead sesquioxide, PbiO,. has been shown not to exist as a stable phase. 

B. C. Dutt and S. N. Sen found that when nitric oxide is passed into a suspension of barium dioxide in water, barium nitrite, not nitrate, is formed. P. Sabatier and J. B. Senderens observed no change when nitric oxide is passed over Cuprous Oxide at 500°. H. A. Auden and G. J. Fowler observed that dry nitric oxide and Silver oxide, at ordinary temp., form silver and silver nitrate P. Sabatier and J. B. Senderens also obtained silver and silver nitrite by passing nitric oxide into water with silver oxide in suspension. C. F. Schonbein found gold oxide is reduced by moist nitric oxide, forming nitrous acid. P. Sabatier and J. B. Senderens found that titanium sesquioxide forms white titanic oxide when heated in an atm. of nitric oxide and that stannous oxide below 500° burns in an atm. of nitric oxide, forming stannic oxide. If nitric oxide be passed into water with lead dioxide in suspension, the water is coloured, and in about 3 hrs., lead nitrite and nitrate are formed, and later, rhombic crystals of a basic nitrite. B. C. Dutt and S. N. Sen said that the nitrate is formed by the action of the dioxide on the nitrite. Lead dioxide is reduced to lead oxide by nitric oxide at 315°, and H. A. Auden and G. J. Fowler found that the reaction begins at 15°, when a basic lead nitrite is... 

The structure of platinum dioxide and its reactions with some di, tri, and tetravalent metal oxides have been investigated. Ternary platinum oxides were synthesized at high pressure (40 kUobars) and temperature (to 1600°C). Properties of the systems were studied by x-ray, thermal analysis, and infrared methods. Complete miscibility is observed in most PtO2-rutile-type oxide systems, but no miscibility or compound formation is found with fluorite dioxides. Lead dioxide reacts with Pt02 to form cubic Pb2Pt207. Several corundum-type sesquioxides exhibit measurable solubility in PtOz. Two series of compounds are formed with metal monoxides M2PtOh (where M is Mg, Zn, Cd) and MPt306 (where M is Mg, Co, Ni, Cu, Zn, Cd, and Hg). 

A2Pt207, similar to those reported for tin, ruthenium, titanium, and several other tetravalent ions. Trivalent ions which form cubic platinum pyrochlores range from Sc(III) at 0.87 A to Pr(III) at X.14 A. Distorted pyrochlore structures are formed by lanthanum (1.18 A) and by bismuth (1.11 A). Platinum dioxide oxidizes Sb203 to Sb2(>4 at high pressure. The infrared spectra and thermal stability of the rare earth platinates have been reported previously and will not be repeated here, except to point out the rather remarkable thermal stability of these compounds decomposition to the rare earth sesquioxide and platinum requires temperatures in excess of 1200 °C. 

The existence of five oxides of palladium has at various times been postulated, namely, the suboxide, Pd20 penta palladium hexoxide, Pd506 the monoxide, PdO the dioxide, Pd02, and the sesquioxide, PdgOa-... 

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