Vapour phase mechanism

There is a qualitative distinction between these two types of mass transfer. In the case of vapour phase transport, matter is subtracted from the exposed faces of the particles via dre gas phase at a rate determined by the vapour pressure of the solid, and deposited in the necks. In solid state sintering atoms are removed from the surface and the interior of the particles via the various diffusion vacancy-exchange mechanisms, and the centre-to-cenU e distance of two particles undergoing sintering decreases with time. 

In which the ratio m/n is close to 3. The silane was produced by free radical copolymerization of vinyltriethoxysilane with N-vinylpyrrolidone. Its number-average molecular weight evaluated by vapour-phase osmometry was 3500. Porous silica microballs with a mean pore diameter of 225 A, a specific surface area (Ssp) of 130 m2/g and a pore volume of 0.8 cm3/g were modified by the silane dissolved in dry toluene. After washings and drying, 0.55% by weight of nitrogen and 4.65% of carbon remained on the microballs. Chromatographic tests carried out with a series of proteins have proved the size-exclusion mechanism of their separation. 

These dyes have affinity for one or, usually, more types of hydrophobic fibre and they are normally applied by exhaustion from fine aqueous dispersion. Although pure disperse dyes have extremely low solubility in cold water, such dyes nevertheless do dissolve to a limited extent in aqueous surfactant solutions at typical dyeing temperatures. The fibre is believed to sorb dye from this dilute aqueous solution phase, which is continuously replenished by rapid dissolution of particles from suspension. Alternatively, hydrophobic fibres can absorb disperse dyes from the vapour phase. This mechanism is the basis of many continuous dyeing and printing methods of application of these dyes. The requirements and limitations of disperse dyes on cellulose acetate, triacetate, polyester, nylon and other synthetic fibres will be discussed more fully in Chapter 3. Similar products have been employed in the surface coloration of certain thermoplastics, including cellulose acetate, poly(methyl methacrylate) and polystyrene. 

These materials are very easily autoxidised and often have a low autoignition temperature. It is reported that many of the less volatile liquid aldehydes will eventually inflame if left exposed to air on an absorbent surface. The mechanism is undoubtedly similar to that giving rise to easy ignition in the air-oxidation of acetaldehyde and propionaldehyde initial formation of a peroxy-acid which catalyses the further oxidation[l]. Autoignition temperatures of lower aldehydes are much reduced by pressure, but appear to depend little on oxygen content. The effect is worst in the presence of free liquid, in which initial oxidation appears to occur, possibly catalysed by iron, followed by ignition of the vapour phase [2], An acetaldehyde/rust mix exploded at room temperature on increasing the air pressure to 7 bar. 

Korai (2001) also considered the importance of density profile of composites made from acetylated fibres in determining mechanical properties. Fibres of yellow cedar were acetylated with vapour-phase acetic anhydride and fibreboards were made from these, bonded with melamine formaldehyde resin. The results from this study indicated that bonding between fibres was the most important property determining mechanical properties. 

The vapour phase nitration of hydrocarbons proceeds via a radical mechanism and so it is found that tertiary carbon centres are nitrated most readily, followed by secondary and primary... 

Figure 5.6 Combustion mechanism for vapour phase diffusion flame.

On the other hand, n-alkanes (n = 4, 6, 7) adsorbed from the vapour phase on Ag(lll) surfaces also grow following the Stranski-Krastanov mechanism (Wu et al, 2001). 

The mechanism of growth of the films may be modelled by considering that the vapour phase transported to the substrate initially condenses in an amorphous state... 

The mechanisms of droplet (or liquid germs) formation from a supersaturated vapour phase is still the subject of many investigations. After giving a brief account of the classical theory [64], which, as shown above, provides a simple method for estimating the energy barrier to overcome before effective nucleation is started, and permits the estimation of the critical cluster size, a complementary approach will be presented. 

D. Mercury photosensitized reations. Mercury atoms are frequently used as photosensitizers in vapour phase reactions. The mechanisms involved are... 

Aluminum methoxide Al(OMe)3 is a solid which sublimes at 240 °C in vacuum. Aluminum isopropoxide melts in the range 120-140 °C to a viscous liquid which readily supercools. When first prepared, spectroscopic and X-ray evidence indicates a trimeric structure which slowly transforms to a tetramer in which the central Al is octahedrally coordinated and the three peripheral units are tetrahedral.162,153 Intramolecular exchange of terminal and bridging groups, which is rapid in the trimeric form, becomes very slow in the tetramer. There is MS and other evidence that the tetramer maintains its identity in the vapour phase.164 Al[OCH(CF3)2]3 is more volatile than Al[OCH(Me)2]3 and the vapour consists of monomers.165 Aluminum alkoxides, particularly Al(OPr )3, have useful catalytic applications in the synthetic chemistry of aldehydes, ketones and acetals, e.g. in the Tishchenko reaction of aldehydes, in Meerwein-Pondorf-Verley reduction and in Oppenauer oxidation. The mechanism is believed to involve hydride transfer between RjHCO ligands and coordinated R2C=0— A1 groups on the same Al atom.1... 

A rate and equilibrium study of the cis/trans isomerization of tris(l,l,l-trifluoro-2,4-pentanedionato)chromium(III) in the vapour phase has been reported.761 The equilibrium constant 3.56 was independent of temperature in the range 118-144.8 °C, the same value being measured by both static and kinetic methods. The activation energies for isomerization were both less than 115 kJmol-1 the Cr—O bond energy is 210 kJ mol-1. On these grounds, a bond-rupture mechanism was rejected. A similar mechanism may operate for the isomerization in solution. 

With an inorganic catalyst (Ag20/Al203 [307]) a simple surface process is assumed for the vapour phase hydration water adsorbed on the surface of silver oxide reacts with gaseous ethylene oxide to form adsorbed glycol which is then desorbed this is obviously an oversimplification of the actual mechanism. 

---