Catalytic effects

Gluconic acid and other hydroxy acids act similarly. Sequestering agents are used extensively, e.g. for preventing deleterious catalytic effects of traces of Fe or Cu and in analysis. 

Sometimes a large proportion of sulphuric acid is employed (see below under esters of dibasic acids). The good yields thus obtained are partially due to the removal of water by the acid as well as to the catalytic effect. 

Clearly, under homogeneous conditions, no significant catalytic effect is observed. Note that we have... 

The kinetic data are essentially always treated using the pseudophase model, regarding the micellar solution as consisting of two separate phases. The simplest case of micellar catalysis applies to unimolecTilar reactions where the catalytic effect depends on the efficiency of bindirg of the reactant to the micelle (quantified by the partition coefficient, P) and the rate constant of the reaction in the micellar pseudophase (k ) and in the aqueous phase (k ). Menger and Portnoy have developed a model, treating micelles as enzyme-like particles, that allows the evaluation of all three parameters from the dependence of the observed rate constant on the concentration of surfactant". ... 

The catalytic effect on unimolecular reactions can be attributed exclusively to the local medium effect. For more complicated bimolecular or higher-order reactions, the rate of the reaction is affected by an additional parameter the local concentration of the reacting species in or at the micelle. Also for higher-order reactions the pseudophase model is usually adopted (Figure 5.2). However, in these systems the dependence of the rate on the concentration of surfactant does not allow direct estimation of all of the rate constants and partition coefficients involved. Generally independent assessment of at least one of the partition coefficients is required before the other relevant parameters can be accessed. 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

Despite the fact that solutions of acetyl nitrate prepared from purified nitric acid contained no detectable nitrous acid, the sensitivity of the rates of nitration of very reactive compounds to nitrous acid demonstrated in this work is so great that concentrations of nitrous acid below the detectable level could produce considerable catalytic effects. However, because the concentration of nitrous acid in these solutions is unknown the possibility cannot absolutely be excluded that the special mechanism is nitration by a relatively unreactive electrophile. Whatever the nature of the supervenient reaction, it is clear that there is at least a dichotomy in the mechanism of nitration for very reactive compounds, and that, unless the contributions of the separate mechanisms can be distinguished, quantitative comparisons of reactivity are meaningless. 

Sandell and KolthofP developed a quantitative method for iodide based on its catalytic effect on the following redox reaction. 

Stabilizers and pigments are normally slurried with macroglycol and added to the polymeric glycol charge, prior to diisocyanate addition. Therefore, care must be taken to avoid additives that react significantly with diisocyanates or diamines under processing conditions. Also, stabilizers should be chosen that have no adverse catalytic effect on the prepolymer or chain-extension reactions. 

Alternatively the alkylated aromatic products may rearrange. -Butylbenzene [104-57-8] is readily isomerized to isobutylbenzene [538-93-2] and j Abutyl-benzene [135-98-8] under the catalytic effect of Friedel-Crafts catalysts. The tendency toward rearrangement depends on the alkylatiag ageat and the reaction conditions (catalyst, solvent, temperature, etc). 

H2SnClg 6H20, CISO H + CH OH, CH COOH, as well as ben2ene-, naphthalene-, and -toluenesulfonic acids (44). Zinc chloride is probably the most frequentiy used catalyst. Its activity is sometimes increased by fusion with a small amount of aluminum chloride. In other instances, however, sufficient catalytic effect is obtained with a mineral acid alone. 

When the operating temperature exceeds ca 93°C, the catalytic effects of metals become an important factor in promoting oil oxidation. Inhibitors that reduce this catalytic effect usually react with the surfaces of the metals to form protective coatings (see Metal surface treatments). Typical metal deactivators are the zinc dithiophosphates which also decompose hydroperoxides at temperatures above 93°C. Other metal deactivators include triazole and thiodiazole derivatives. Some copper salts intentionally put into lubricants counteract or reduce the catalytic effect of metals. 

Diborane [19287-45-7] the first hydroborating agent studied, reacts sluggishly with olefins in the gas phase (14,15). In the presence of weak Lewis bases, eg, ethers and sulfides, it undergoes rapid reaction at room temperature or even below 0°C (16—18). The catalytic effect of these compounds on the hydroboration reaction is attributed to the formation of monomeric borane complexes from the borane dimer, eg, borane-tetrahydrofuran [14044-65-6] (1) or borane—dimethyl sulfide [13292-87-0] (2) (19—21). Stronger complexes formed by amines react with olefins at elevated temperatures (22—24). 

For environmental reasons, burning should be smokeless. Long-chain and unsaturated hydrocarbons crack in the flame producing soot. Steam injection helps to produce clean burning by eliminating carbon through the water gas reaction. The quantity of steam required can be as high as 0.05—0.3 kg steam per kg of gas burned. A multijet flare can also be used in which the gas bums from a number of small nozzles parallel to radiant refractory rods which provide a hot surface catalytic effect to aid combustion. 

Organic amines, eg, pyridine and piperidine, have also been used successfully as catalysts in the reactions of organosilanes with alcohols and silanols. The reactions of organosilanes with organosilanols lead to formation of siloxane bonds. Nickel, zinc, and tin also exhibit a catalytic effect. 

Chelation itself is sometimes useful in directing the course of synthesis. This is called the template effect (37). The presence of a suitable metal ion facihtates the preparation of the crown ethers, porphyrins, and similar heteroatom macrocycHc compounds. Coordination of the heteroatoms about the metal orients the end groups of the reactants for ring closure. The product is the chelate from which the metal may be removed by a suitable method. In other catalytic effects, reactive centers may be brought into close proximity, charge or bond strain effects may be created, or electron transfers may be made possible. 

Refining and Isomerization. Whatever chlorination process is used, the cmde product is separated by distillation. In successive steps, residual butadiene is stripped for recycle, impurities boiling between butadiene (—5° C) and 3,4-dichloto-l-butene [760-23-6] (123°C) are separated and discarded, the 3,4 isomer is produced, and 1,4 isomers (140—150°C) are separated from higher boiling by-products. Distillation is typically carried out continuously at reduced pressure in corrosion-resistant columns. Ferrous materials are avoided because of catalytic effects of dissolved metal as well as unacceptable corrosion rates. Nickel is satisfactory as long as the process streams are kept extremely dry. 

The catalytic effect of solid particles (as ia heterogeneous nucleation) is to reduce the energy barrier to formation of a new phase. This, in effect, can reduce the interfacial energy O significantly. 

The anion used to prepare the metal soap determines to a large extent whether it will meet fundamental requirements, which can be summed up as follows solubihty and stabiUty ia various kiads of vehicles (this excludes the use of short-chain acids) good storage stabiUty low viscosity, making handling the material easier optimal catalytic effect and best cost/performance ratio. 

There are at least two mechanisms available for aziridine cis-trans isomerism. The first is base-catalyzed and proceeds via an intermediate carbanion (235). The second mechanism can be either thermally or photochemically initiated and proceeds by way of an intermediate azomethine ylide. The absence of a catalytic effect and interception of the 1,3-dipole intermediate provide support for this route. A variety of aziridinyl ketones have been found to undergo equilibration when subjected to base-catalyzed conditions (65JA1050). In most of these cases the cis isomer is more stable than the trans. Base-catalyzed isotope exchange has also been observed in at least one molecule which lacks a stabilizing carbonyl group (72TL3591). 

Product Quality Considerations of product quahty may require low holdup time and low-temperature operation to avoid thermal degradation. The low holdup time eliminates some types of evaporators, and some types are also eliminated because of poor heat-transfer charac teristics at low temperature. Product quality may also dic tate special materials of construction to avoid met hc contamination or a catalytic effect on decomposition of the product. Corrosion may also influence evaporator selection, since the advantages of evaporators having high heat-transfer coefficients are more apparent when expensive materials of construction are indicated. Corrosion and erosion are frequently more severe in evaporators than in other types of equipment because of the high hquid and vapor velocities used, the frequent presence of sohds in suspension, and the necessary concentration differences. 

Kinds of Catalysts To a certain extent it is known what lands of reactions are speeded up by certain classes of catalysts, but individual members of the same class may differ greatly in activity, selectivity, resistance to deactivation, and cost. Since solid catalysts are not particularly selective, there is considerable crossing of lines in the classification of catalysts and the kinds of reactions they favor. Although some trade secrets are undoubtedly employed to obtain marginal improvements, the principal catalytic effects are known in many cases. 

It was found that sorbed palladium might catalyse reaction of Mn(III) reduction by Cf not only after it s removing from coal, but AC with palladium, Pd/AC, has also his own catalytic effect. On the base of dependence between characteristics of AC, chemical state of palladium on AC surface and catalytic action of Pd/AC in indicator reaction it might establish, that catalytic action concerns only to non-reduced or partly reduced palladium ions connected with chloride ions on coal surface. The presence or absence of catalytic action of Pd/AC in above-mentioned reaction may be proposed for determination of chemical state of palladium on AC surface. Catalytic effect was also used for palladium micro-amounts determination by soi ption-catalytic method. 

The determination of organic compounds by their direct catalytic effect on indicator reaction rates is a relatively unexplored ai ea promising valuable analytical chai acteristics, as we have recently shown in the determination of traces of unsymmetrical dimethylhydrazine (UDMH) by the oxidation of 3,3, 5,5 -tetramethylbenzidine (TMB) by atmospheric oxygen initiated with persulfate [1]. 

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