Water vapour formation

An analysis of the rate of CO, CO2 and H2O evolution during TPO of industrial and laboratory coked cracking catalysts has provided information on the mechanism and energetics of coke combustion. The mechanism has been deduced from previously reported studies on amorphous carbon oxidation [8], while rate parameters have been calculated from non-linear regression simulations of the TPO spectra. The rate of water vapour formation has not been analysed due to re-adsorption expected to affect the apparent kinetics. "Soft" and "hard" coke have been identified in the spectra, and oxidation activation energies of each compared. A further outcome of this work is the proposal that coke deposition on cracking catalysts proceeds from "soft" to "hard" coke via a series of dehydrogenation or dehydration steps. 

Product Structure A feature frequently observed in the decomposition of crystalline hydrates, which has not yet been given a convincing interpretation in the framework of universally accepted ideas, is the formation of solid products in either an amorphous or a crystalline state, depending on the actual water vapour pressure in the reactor. This phenomenon was observed by Kohlschiitter and Nitschmann in 1931 [35] and has been the subject of numerous publications, including the study of Volmer and Seydel [36], who used it as a basis for explaining the Topley-Smith (T-S) effect, and a series of articles by Frost et al. [37-39]. Dehydration of many crystalline hydrates in vacuum entails formation of an X-ray amorphous (finely dispersed) residue and, in the presence of water vapour, formation of a crystalline product. The highest H2O pressure at which an amorphous product can still form varies for different hydrates from a few tenths to a few Torr (Table 2.4). As the decomposition temperature increases, the boundary of formation of the crystalline product shifts towards higher H2O pressures. 

When the current is decreased, the combined effect of the changes in the partial pressures and the polarisation losses results in the increase of the cell voltage. It is observed that the cell voltage initially overshoots before settling to a steady-state value. The FU and the OU, which are proportional to the current, also decrease. The reverse phenomena are observed with the increase in the external load current. The sudden decrease in the load current results in the decrease in the rate of hydrogen and oxygen consumption and the rate of water vapour formation. In other words, the... 

If produced gas contains water vapour it may have to be dried (dehydrated). Water condensation in the process facilities can lead to hydrate formation and may cause corrosion (pipelines are particularly vulnerable) in the presence of carbon dioxide and hydrogen sulphide. Hydrates are formed by physical bonding between water and the lighter components in natural gas. They can plug pipes and process equipment. Charts such as the one below are available to predict when hydrate formation may become a problem. 

Dehydration can be performed by a number of methods cooling, absorption and adsorption. Water removal by cooling is simply a condensation process at lower temperatures the gas can hold less water vapour. This method of dehydration is often used when gas has to be cooled to recover heavy hydrocarbons. Inhibitors such as glycol may have to be injected upstream of the chillers to prevent hydrate formation. 

The presence of water vapour in the ingoing gas irrixmre has been found to suppress the formation of graphite and dins to favour diamond formation. The significant change in composition when water vapour is added, is the presence of carbon monoxide in about half the proportion of hydrogen atoms. 

Consider Ni exposed to Oj/HjO vapour mixtures. Possible oxidation products are NiO and Ni (OH)2, but the large molar volume of Ni (OH)2, (24 cm compared with that of Ni, 6.6 cm ) means that the hydroxide is not likely to form as a continuous film. From thermodynamic data, Ni (OH)2 is the stable species in pure water vapour, and in all Oj/HjO vapour mixtures in which O2 is present in measurable quantities, and certainly if the partial pressure of O2 is greater than the dissociation pressure of NiO. But the actual reaction product is determined by kinetics, not by thermodynamics, and because the mechanism of hydroxide formation is more complex than oxide formation, Ni (OH)2 is only expected to form in the later stages of the oxidation at the NiO/gas interface. As it does so, cation vacancies are formed in the oxide according to... 

Water vapour is essential to the formation of an electrolyte solution which will support the electrochemical corrosion reactions, and its concentration in the atmosphere is usually expressed in terms of the relative humidity (r.h.). 

Secondly, absorbent particles such as charcoal and soot are intrinsically inert but have surfaces or infrastructures that adsorb SO, and by either coadsorption of water vapour or condensation of water within the structure, catalyse the formation of a corrosive acid electrolyte solution. Dirt with soot assists the formation of patinae on copper and its alloys by retaining soluble corrosion products long enough for them to be converted to protective, insoluble basic salts. 

For Fe in steam, water vapour or COj below 570°C, a two-layered Fej04 layer is observed, the inner layer growing by Oj diffusion inwards. Similarly, Potter and Mann reported the formation of a duplex Fej04 layer during the oxidation of mild steel in steam between 300°C and 550°C. 

Bircumshaw and Edwards [1029] showed that the rate of nickel formate decomposition was sensitive to reactant disposition, being relatively greater for the spread reactant, a—Time curves were sigmoid and obeyed the Prout—Tompkins equation [eqn. (9)] with values of E for spread and aggregated powder samples of 95 and 110 kJ mole-1, respectively. These values are somewhat smaller than those subsequently found [375]. The decreased rate observed for packed reactant was ascribed to an inhibiting effect of water vapour which was most pronounced during the early stages. 

As already indicated, the difficulty of reducing supported iron in hydrogen is well-known [6,8,11]. It probably arises from a combination of causes, the two most important of which are a strong interaction with the support [6,8] and reoxidation or inhibition by water vapour in the pores of the oxide [14]. With MgO as support, there is undoubtedly a strong tendency for iron, especially at the Fe2+ stage of reduction, to be present at least in part as FeO-MgO (Fe Mgi.jjO) solid solution [6,8]. This need not be deleterious to the ultimate formation of finely-divided iron, provided the method of preparation has led to a solid solution in which the Fe2+ ions are well-distributed. The iron particles are limited in size... 

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