Transition-metal oxides hydrogen

Reaction with Meta/ Oxides. The reaction of hydrogen chloride with the transition-metal oxides at elevated temperatures has been studied extensively. Fe202 reacts readily at temperatures as low as 300°C to produce FeCl and water. The heavier transition-metal oxides require a higher reaction temperature, and the primary reaction product is usually the corresponding oxychlorides. Similar reactions are reported for many other metal oxides, such as Sb202, BeO, AI2O2, andTi02, which lead to the formation of relatively volatile chlorides or oxychlorides. 

Alcohol autoxidation is carried out in the range of 70—160°C and 1000—2000 kPa (10—20 atm). These conditions maintain the product and reactants as Hquids and are near optimum for practical hydrogen peroxide production rates. Several additives including acids, nitriles, stabHizers, and sequestered transition-metal oxides reportedly improve process economics. The product mixture, containing hydrogen peroxide, water, acetone, and residual isopropyl alcohol, is separated in a wiped film evaporator. The organics and water are taken overhead and further refined to recover by-product acetone and the... 

Metal hydrides containing transition metal (TM)-hydrogen complexes, with the transition metal in a formally low oxidation state, are of fundamental interest for clarifying how an electron-rich metal atom can be stabilized without access to the conventional mechanism for relieving the electron density by back-donation to suitable ligand orbitals. By reacting electropositive alkali or alkaline earth metals ( -elements) with group 7, 8, 9, and 10 transition metals in... 

In an optimally controlled process free from transition-metal ions hydrogen peroxide bleaching is remarkably safe, there being no reported detrimental effects of bleaching at around 100 °C or for more than several hours [143]. Under such conditions, most of the peroxide appears to be consumed in the oxidation of chain end units of the cellulose macromolecule. The other major effect on the substrate is oxidation of secondary hydroxy to keto groups, accompanied by the formation of very few aldehyde or carboxyl groups [235]. 

The hydrogen-bonding interactions within the complexes W2CI4-(y-OR)2(OR)2(ROH)2 and V Cli y-OR)2(ORT)2(Rf0H)2 may provide the molecular analogues with which to model the structure and reactivities of transition metal oxide catalysts that possess surface hydroxyl groups. The thermal treatment which is often carried out in the pretreatment of metal oxides (leading to the loss of -OH... 

The reactions of MeOH with some transition metal oxide cluster anions [M O J, where M = Mn, Fe, Co, Ni, Cu n = 1,2 x = 2—4, have been studied (254). The [M03] anions were unreactive toward MeOH, unlike [Nb03]. The addition of the hydrogen molecule to the other cluster anions was the common reaction yielding the following transformations,... 

THE HYDROGEN STORAGE BEHAVIOUR OF PT AND PD LOADED TRANSITION METAL OXIDES... 

The Hydrogen Storage Behaviour of Pt and Pd Loaded Transition Metal Oxides... 

We turn now to an evaluation of nc, the concentration of centres at which the transition occurs. We remark first of all that an experimental value is difficult to obtain. We do not know of a crystalline system, with one electron per centre in an s-state, that shows a Mott transition. Figure 5.3 in the next chapter shows the well-known plot given by Edwards and Sienko (1978) for nc versus the hydrogen radius aH for a large number of doped semiconductors, giving ncaH=0.26. In all of these the positions of the donors are random, and it is now believed that for many, if not all, the transition is of Anderson type. In fluid caesium and metal-ammonia solutions the two-phase region is expected, but this is complicated by the tendency of one-electron centres to form diamagnetic pairs (as they do in V02). In the Mott transition in transitional-metal oxides the electrons are in d-states. 

Let us analyze the observed rate orders for hydrogen oxidation on Group IV transition metal oxides. For the steps of the detailed mechanism in accordance with refs. 38, 48, and 49, see eqn. (53) the appropriate kinetic equation is given by eqn. (54). 

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