Addition vapor phase

Diffusion at 1000-1100°C gives erratic results while causing damage to the Si surface. Random pitting results, suggesting enhanced reactions at surface defect sites. In the presence of low concentrations of O2, additional vapor phase reactions occur ... 

Obviously, the nature of the reaction under these conditions will differ from the reaction in the presence of a carrier insofar as there is a direct reaction between the hydrogen and the coal. In addition, vapor-phase (or secondary) hydrogenation may also follow the primary hydrogenation in which volatile products from the decomposition of the coal or from the reaction of the coal with hydrogen then react with more hydrogen to modify the slate of primary reaction products. 

Two additional illustrations are given in Figures 6 and 7 which show fugacity coefficients for two binary systems along the vapor-liquid saturation curve at a total pressure of 1 atm. These results are based on the chemical theory of vapor-phase imperfection and on experimental vapor-liquid equilibrium data for the binary systems. In the system formic acid (1) - acetic acid (2), <() (for y = 1) is lower than formic acid at 100.5°C has a stronger tendency to dimerize than does acetic acid at 118.2°C. Since strong dimerization occurs between all three possible pairs, (fij and not... 

Reactions with Aldehydes and Ketones. The base-catalyzed self-addition of acetaldehyde leads to formation of the dimer, acetaldol [107-89-1/, which can be hydrogenated to form 1,3-butanediol [107-88-0] or dehydrated to form crotonaldehyde [4170-30-3]. Crotonaldehyde can also be made directiy by the vapor-phase condensation of acetaldehyde over a catalyst (53). 

Mercaptals, CH2CH(SR)2, are formed in a like manner by the addition of mercaptans. The formation of acetals by noncatalytic vapor-phase reactions of acetaldehyde and various alcohols at 35°C has been reported (67). Butadiene [106-99-0] can be made by the reaction of acetaldehyde and ethyl alcohol at temperatures above 300°C over a tantala—siUca catalyst (68). Aldol and crotonaldehyde are beheved to be intermediates. Butyl acetate [123-86-4] has been prepared by the catalytic reaction of acetaldehyde with 1-butanol [71-36-3] at 300°C (69). 

Liquid- and vapor-phase processes have been described the latter appear to be advantageous. Supported cadmium, zinc, or mercury salts are used as catalysts. In 1963 it was estimated that 85% of U.S. vinyl acetate capacity was based on acetylene, but it has been completely replaced since about 1982 by newer technology using oxidative addition of acetic acid to ethylene (2) (see Vinyl polymers). In western Europe production of vinyl acetate from acetylene stiU remains a significant commercial route. 

Vapor-Phase Condensations of Acetic Acid or Esters with Formaldehyde. Addition of a methylol group to the a-carbon of acetic acid or esters, foUowed by dehydration, gives the acrylates. 

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. 

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). 

Zeohtes have recendy been employed as soHd catalysts for the vapor-phase nitration of aromatics with nitric acid. Additional research is required to improve yields and to niinimi2e loss of catalytic activity as the nitration progresses (see Molecularsieves). 

Flame Retardants. Flame retardants are added to nylon to eliminate burning drips and to obtain short self-extinguishing times. Halogenated organics, together with catalysts such as antimony trioxide, are commonly used to give free-radical suppression in the vapor phase, thus inhibiting the combustion process. Some common additives are decabromodiphenyl oxide, brominated polystyrene, and chlorinated... 

The formation of pyridine derivatives from a, P-unsaturated aldehydes and ammonia involves formation of three bonds during the ring synthesis. For example, with an a, P-unsaturated aldehyde, both 2,5-substituted as well as 3,4-substituted pyridines can be obtained, depending on whether a 1,2- (eq. 17) or 1,4-addition (eq. 18) occurs with ammonia. Reactions are performed in the vapor phase with catalysts. 

Complex ions of Th(IV) have been studied and include M2 ThClg] [21493-66-3] where M = Li—Cs, (CH2)4N, or (C2H ) N. Under more extreme conditions, eg, molten KCl or vapor phase, ThCL [51340-85-3] ThCh [51340-84-2] ThCl g [53565-25-6] and ThCh are known to be important. Additional information on thorium chlorides can be found in the Hterature (81). 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

The ultraviolet lamps used in the photochlorination process serve to dissociate the chlorine into free radicals and start the radical-chain reaction. Other radical sources, such as 2,2 -a2obisisobutyronitrile, have been used (63,64). Primary by-products of the photochlorination process include 1,1,2-trichloroethane (15—20%), tetrachloroethanes, and pentachloroethane. Selectivity to 1,1,1-trichloroethane is higher in vapor-phase chlorination. Various additives, most containing iodine or an aromatic ring in the molecule, have been used to increase the selectivity of the reaction to... 

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. 

Precipitation and Vapor-Phase Inhibitors. Precipitation inhibitors are film-forming compounds that produce barrier films over the entire surface. Phosphates and siUcates, which are the most common, do not provide the degree of protection afforded by chromate inhibitors, but are useful in situations where nontoxic additives are required. Two main drawbacks to the use of phosphates and siUcates are the dependence on the water composition and the control required to achieve maximum inhibition (37,38). 

Fig. 1. Vapor pressure and relative humidity over CaCl solutions and solids. The straight horizontal lines ia the right-hand portion represent two soHd phases and a gas phase for vertical line iatersections. In addition, a soHd phase, saturated solution, and a vapor phase occur ia the regions between the vertical lines. The lower left-hand corner shows the ice solution line. The region ia between, with skewed isothermal lines, represents unsaturated solutions ...

Ethyl Vinyl Ether. The addition of ethanol to acetylene gives ethyl vinyl ether [104-92-2] (351—355). The vapor-phase reaction is generally mn at 1.38—2.07 MPa (13.6—20.4 atm) and temperatures of 160—180°C with alkaline catalysts such as potassium hydroxide and potassium ethoxide. High molecular weight polymers of ethyl vinyl ether are used for pressure-sensitive adhesives, viscosity-index improvers, coatings and films lower molecular weight polymers are plasticizers and resin modifiers. 

Addition of 15% gasoline to methanol to produce M85 fuel is an alternative. At temperatures above —6.7° C, reHable ignition of M85 fuel occurs because the gasoline provides the vapor phase necessary for ignition under choked condition. 

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