Sulphur adsorption

Fig 14 (A) Early stages of sulphur adsorption on the stripped Cu layer. Individual sulphur... 

Wilde et al.120 and Paal121 consider that metal-sulphur bonds are stronger than metal-carbon bonds, and that sulphur can displace carbon from Pt. The strength of irreversible sulphur adsorption is in the order Re > Pt-Re > Pt. 

The dynamics of sulphur uptake in a prereformer is like a fixed-bed absorption as seen in a zinc-oxide bed (refer to Chapter 1). However, in a tubular reformer the pore diffusion restrictions in the sulphur adsorption in a single pellet has a complex influence on the transient sulphur profiles in the reactor and a mathematical model [112] [387] [389] is required to evaluate more exactly the time for fiill saturation and the breakthrough curves of sulphur. 

Gases which are high in FIjS are subject to a de-sulphurisation process in which H2S is converted into elemental sulphur or a metal sulphide. There are a number of processes based on absorption in contactors, adsorption (to a surface) in molecular sieves or chemical reaction (e.g. with zinc oxide). 

Stouffer J M and McCarthy T J 1988 Polymer monolayers prepared by the spontaneous adsorption of sulphur-functionalized polystyrene on gold surfaces Macromolecules 2 1204-8... 

Stouffer J M and McCarthy T J 1986 Self-assembly of sulphur functionalization on the adsorption of polystyrene on gold Polym. Prepr. 27(2) 242-5... 

In sulphur dioxide linear kinetics are generally observed due to control by phase boundary reactions, i.e. adsorption of SOj. RahmeF suggested that this is one of the conditions which favours simultaneous nucleation of sulphide and oxide at the gas/scale interface. The main reaction products are NiO, NijSj, Ni-S,j, and NiS04, depending on the temperature and gas pressure for example, according to the following reaction ... 

Sulphur Trioxide (SO2 -I- O2) Linear reaction rates are observed due to phase boundary control by adsorption of the reactant, SO3. Maximum rates of reaction occur at a SO2/O2 ratio of 2 1 where the SO3 partial pressure is also at a maximum. With increasing 02 S02 ratio the kinetics change from linear to parabolic and ultimately, of course, approach the behaviour of the Ni/NiO system. At constant gas composition and pressure, the reaction also reaches a maximum with increasing temperature due to the decreasing SO3 partial pressure with increasing temperature, so that NiS04 formation is no longer possible and the reaction rate falls. 

Blocking of reaction sites The interaction of adsorbed inhibitors with surface metal atoms may prevent these metal atoms from participating in either the anodic or cathodic reactions of corrosion. This simple blocking effect decreases the number of surface metal atoms at which these reactions can occur, and hence the rates of these reactions, in proportion to the extent of adsorption. The mechanisms of the reactions are not affected and the Tafel slopes of the polarisation curves remain unchanged. Behaviour of this type has been observed for iron in sulphuric acid solutions containing 2,6-dimethyl quinoline, /3-naphthoquinoline , or aliphatic sulphides . 

Y. Matsumoto, T. Onishi, and K. Tamam, Effects of Sulphur on a Palladium Surface on the Adsorption of Carbon Monoxide and the Adsorption and decomposition of nitric oxide, J.C.S. Faraday I 76, 1116-1121 (1980). 

Eeliu JM, Orts JM, Gomez R, Aldaz A, Claviher J. 1994. New information on the unusual adsorption states of Pt(l 11) in sulphuric acid solutions from potentiostatic adsorbate replacement by CO. J Electroanal Chem 372 265-268. 

Christensen PA, Hamnett A, Weeks S A. 1988. In-situ FTIR study of adsorption and oxidation of methanol on platinum and platinized glassy carbon electrodes in sulphuric acid solution. J Electroanal Chem 250 127-142. 

Electroneutral substances that are less polar than the solvent and also those that exhibit a tendency to interact chemically with the electrode surface, e.g. substances containing sulphur (thiourea, etc.), are adsorbed on the electrode. During adsorption, solvent molecules in the compact layer are replaced by molecules of the adsorbed substance, called surface-active substance (surfactant).t The effect of adsorption on the individual electrocapillary terms can best be expressed in terms of the difference of these quantities for the original (base) electrolyte and for the same electrolyte in the presence of surfactants. Figure 4.7 schematically depicts this dependence for the interfacial tension, surface electrode charge and differential capacity and also the dependence of the surface excess on the potential. It can be seen that, at sufficiently positive or negative potentials, the surfactant is completely desorbed from the electrode. The strong electric field leads to replacement of the less polar particles of the surface-active substance by polar solvent molecules. The desorption potentials are characterized by sharp peaks on the differential capacity curves. 

For molecules with small dipoles, the adsorption region is distributed symmetrically around the potential of the electrocapillary maximum. However, if chemisorption interaction occurs between one end of the dipole (e.g. sulphur in thiourea) and the electrode, the adsorption region is shifted to the negative or positive side of the electrocapillary maximum. 

The sulphur-free syngas has a high C02 concentration and an elevated pressure (2-7 MPa), thus making physical absorption highly recommended for C02 separation, although adsorption process such as pressure swing adsorption (PSA) is also utilised. 

Electrolytes are used to promote the exhaustion of direct or reactive dyes on cellulosic fibres they may also be similarly used with vat or sulphur dyes in their leuco forms. In the case of anionic dyes on wool or nylon, however, their role is different as they are used to facilitate levelling rather than exhaustion. In these cases, addition of electrolyte decreases dye uptake due to the competitive absorption of inorganic anions by the fibre and a decrease in ionic attraction between dye and fibre. In most discussions of the effect of electrolyte on dye sorption, attention is given only to the ionic aspects of interaction. In most cases, this does not create a problem and so most adsorption isotherms of water-soluble dyes are interpreted on the basis of Langmuir or Donnan ionic interactions only. There are, however, some observed cases of apparently anomalous behaviour of dyes with respect to electrolytes that cannot be explained by ionic interactions alone. 

Figure 2.17 Cyclic voltammogram of a Pt electrode immersed in N -saturated aqueous sulphuric acid showing the hydrogen adsorption and desorption peaks.

As was discussed above, it is essential to determine the effect, if any, that the emersion process has on the double layer. To do this, Wilhelm and colleagues have performed the definitive type of blank experiment. CO was adsorbed onto the Pt working electrode from sulphuric acid electrolyte. After adsorption, the CO-saturated solution was replaced with pure electrolyte. The potential of the electrode was then ramped in order to oxidise off the adsorbate, as C02, and the voltammogram so obtained is shown in Figure 2.118(a). The experiment was then repeated CO was adsorbed as before, but the electrode was emersed and transferred into the UHV chamber, before being re-immersed and the potential ramp applied. The voltammogram so... 

Cabrera et al. [95] determined total dissolved and suspended phosphorus in natural waters by a method involving digestion with hydrogen peroxide and sulphuric acid, errors may be caused by adsorption of phosphorus on hydrous iron and aluminium oxides formed during neutralization prior to filtration. It is proposed that this can be prevented by adding extra sulphuric acid after neutralization, to dissolve such oxides and release the adsorbed phosphorus into solution. 

Millson [113] investigated components of sewage sludge and found elementary sulphur in the hydrocarbon fractions eluted from liquid adsorption columns. By using a solid adsorbent such as alumina, silica gel, or Florisil, and heptane as eluent, the sulphur could be separated from weakly adsorbed hydrocarbons, e.g. squalene or biphenyl, but not from more strongly adsorbed hydrocarbons such as phenyldodecane. 

A method [62] has been described for the determination of down to 2.5pg kg-1 alkylmercury compounds and inorganic mercury in river sediments. This method uses steam distillation to separate methylmercury in the distillate and inorganic mercury in the residue. The methylmercury is then determined by flameless atomic absorption spectrophotometry and the inorganic mercury by the same technique after wet digestion with nitric acid and potassium permanganate [63]. The well known adsorptive properties of clays for alkylmercury compounds does not cause a problem in the above method. The presence of humic acid in the sediment did not depress the recovery of alkylmercury compounds by more than 20%. In the presence of metallic sulphides in the sediment sample the recovery of alkylmercury compounds decreased when more than lmg of sulphur was present in the distillate. The addition of 4M hydrochloric acid, instead of 2M hydrochloric acid before distillation completely, eliminated this effect giving a recovery of 90-100%. 

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