Vapor-phase mechanisms

Vapor-Phase Mechanisms. Phosphoms flame retardants can also exert vapor-phase flame-retardant action. Trimethyl phosphate [512-56-1] C H O P, retards the velocity of a methane—oxygen flame with about the same molar efficiency as antimony trichloride (30,31). Both physical and chemical vapor-phase mechanisms have been proposed for the flame-retardant action of certain phosphoms compounds. Physical (endothermic) modes of action have been shown to be of dominant importance in the flame-retardant action of a wide range of non-phosphoms-containing volatile compounds (32). 

Triphenylphosphine oxide [791-28-6], C gH OP, and triphenyl phosphate [115-86-6], C gH O P, as model phosphoms flame retardants were shown by mass spectroscopy to break down in a flame to give small molecular species such as PO, HPO2, and P2 (33—35). The rate-controlling hydrogen atom concentration in the flame was shown spectroscopically to be reduced when these phosphoms species were present, indicating the existence of a vapor-phase mechanism. 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

The question as to whether a flame retardant operates mainly by a condensed-phase mechanism or mainly by a vapor-phase mechanism is especially comphcated in the case of the haloalkyl phosphoms esters. A number of these compounds can volatilize undecomposed or undergo some thermal degradation to release volatile halogenated hydrocarbons (37). The intact compounds or these halogenated hydrocarbons are plausible flame inhibitors. At the same time, thek phosphoms content may remain at least in part as relatively nonvolatile phosphoms acids which are plausible condensed-phase flame retardants (38). There is no evidence for the occasionally postulated formation of phosphoms haUdes. Some evidence has been presented that the endothermic vaporization and heat capacity of the intact chloroalkyl phosphates may be a main part of thek action (39,40). 

Vapor-Phase Mechanisms. Phosphorus flame retardants can also exert vapor-phase llamc-rctardam acliun. Both physical and chemical vapor-phase mechanisms have been proposed lor the flamc-reuirdatit action of certain phosphorus compounds, such as triphenvl phosphate. 

A predominantly vapor-phase mechanism of flame retardation has been proposed for flame retardants based on triphenylphosphine oxide and triphenyl phosphate has been proposed (Scheme 5.1). 

Prins et al. (21) described the lower flammability of poly-bromostyrene relative to that of polystyrene. On the basis of thermal analysis experiments, they suggested that bromine inhibited most of the oxidative chain reactions, and thus the combustion was not supported (vapor-phase mechanism). Khanna and Pearce (16) and Brauman (22) demonstrated that polystyrene could be flame retarded by appropriately modifying its structure with substituents that promote the char yield of the system (condensed-phased mechanism). 

FIGURE 5.10 Stages of CNT filling with fullerene the vapor phase mechanism. 

Chemical routes used to produce ZrB include solutions, reactions with boron-containing polymers, and pre-ceramic pol3uners. Nanocrystalline ZrB has been synthesized by reacting anhydrous chlorides with sodium borohydride (NaBH ) above 500 °C under pressure (Thomson, 1990). The overall process is described by Reaction (6), but the reaction may also proceed by a vapor phase mechanism that involves the decomposition of NaBH to borane (BH3) and its subsequent reaction with a gaseous chloride. ZrB prepared by these routes can have crystallite sizes as small as 10-20 nm ... 

There is, of course, a mass of rather direct evidence on orientation at the liquid-vapor interface, much of which is at least implicit in this chapter and in Chapter IV. The methods of statistical mechanics are applicable to the calculation of surface orientation of assymmetric molecules, usually by introducing an angular dependence to the inter-molecular potential function (see Refs. 67, 68, 77 as examples). Widom has applied a mean-held approximation to a lattice model to predict the tendency of AB molecules to adsorb and orient perpendicular to the interface between phases of AA and BB [78]. In the case of water, a molecular dynamics calculation concluded that the surface dipole density corresponded to a tendency for surface-OH groups to point toward the vapor phase [79]. 

A second Mobil process is the Mobil s Vapor Phase Isomerization Process (MVPI) (125,126). This process was introduced in 1973. Based on information in the patent Hterature (125), the catalyst used in this process is beHeved to be composed of NiHZSM-5 with an alumina binder. The primary mechanism of EB conversion is the disproportionation of two molecules of EB to one molecule of benzene and one molecule of diethylbenzene. EB conversion is about 25—40%, with xylene losses of 2.5—4%. PX is produced at concentration levels of 102—104% of equiHbrium. Temperatures are in the range of 315—370°C, pressure is generally 1480 kPa, the H2/hydrocatbon molar ratio is about 6 1, and WHSV is dependent on temperature, but is in the range of 2—50, although normally it is 5—10. 

The housing physically holds the valve pieces together by means of a mechanical lock (crimp) and fits into the pedestal of the mounting cup. It is made from any of a number of common thermoplastics and contains the metering orifices for both the Hquid and vapor phases of the effluent. Many... 

Either mechanism can be used to describe how antimony—halogen systems operate in both the condensed and vapor phases. In the condensed phase a chat that is formed during the reaction of the polymer, antimony trioxide, and the halogen reduces the rate of decomposition of the polymer therefore, less fuel is available for the flame (16). 

Mechanism. Alumina trihydtate functions as a flame retardant in both the condensed and vapor phases (26). When activated, it decomposes endothermically, eliminating water. 

The mechanism by which tin flame retardants function has not been well defined, but evidence indicates tin functions in both the condensed and vapor phases. In formulations in which there is at least a 4-to-l mole ratio of halogen to tin, reactions similar to those of antimony and halogen are assumed to occur. Volatile stannic tetrahaUde may form and enter the flame to function much in the same manner as does antimony trihaUde. 

Alkyl diphenyl phosphate plasticizers can exert flame-retardant action in vinyl plastics by a condensed-phase mechanism, which is probably some sort of phosphoms acid coating on the char. Triaryl phosphates appear to have a vapor-phase action (29). 

In addition to production of simple monofunctional products in hydrocarbon oxidation there are many complex, multifimctional products that are produced by less weU-understood mechanisms. There are also important influences of reactor and reaction types (plug-flow or batch, back-mixed, vapor-phase, Hquid-phase, catalysts, etc). 

A closer look at the Lewis relation requires an examination of the heat- and mass-transfer mechanisms active in the entire path from the hquid—vapor interface into the bulk of the vapor phase. Such an examination yields the conclusion that, in order for the Lewis relation to hold, eddy diffusivities for heat- and mass-transfer must be equal, as must the thermal and mass diffusivities themselves. This equahty may be expected for simple monatomic and diatomic gases and vapors. Air having small concentrations of water vapor fits these criteria closely. 

A number of theories have been put forth to explain the mechanism of polytype formation (30—36), such as the generation of steps by screw dislocations on single-crystal surfaces that could account for the large number of polytypes formed (30,35,36). The growth of crystals via the vapor phase is beheved to occur by surface nucleation and ledge movement by face specific reactions (37). The soHd-state transformation from one polytype to another is beheved to occur by a layer-displacement mechanism (38) caused by nucleation and expansion of stacking faults in close-packed double layers of Si and C. 

Reaction Mechanism. High temperature vapor-phase chlorination of propylene [115-07-17 is a free-radical mechanism in which substitution of an allyhc hydrogen is favored over addition of chlorine to the double bond. Abstraction of allyhc hydrogen is especially favored since the allyl radical intermediate is stabilized by resonance between two symmetrical stmctures, both of which lead to allyl chloride. 

Vapor-phase inhibitors are volatile compounds that adsorb onto metal surfaces, and retard or prevent corrosion by a variety of mechanisms (37). Inhibitors such as dicyclohexamine nitrate [3882-06-02] can protect a variety of metals such as steel, aluminum, and tinplate. A number of vapor-phase inhibitors are commercially available as powders or tablets. However, vapor-phase inhibitors attack nonferrous metals to varying degrees, thus the manufacturers recommendations should be checked before appHcation. The system to be protected must be closed to maintain the volatile compound, but objects as large as the interior of an ocean-going tanker have been treated by this technique. 

The mechanisms that control dmg deUvery from pumps may be classified as vapor-pressure, electromechanical, or elastomeric. The vapor-pressure controlled implantable system depends on the principle that at a given temperature, a Hquid ia equiUbrium with its vapor phase produces a constant pressure that is iadependent of the enclosing volume. The two-chamber system contains iafusate ia a flexible beUows-type reservoir and the Hquid power source ia a separate chamber (142). The vapor pressure compresses the dmg reservoir causiag dmg release at a constant rate. Dmg maybe added to the reservoir percutaneously via a septum, compressing the fluid vapor iato the Hquid state. 

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