Effect accelerating

Some systems converge poorly, particularly those with multiple bonds or weak interactions between open-shell systems. HyperChem includes two convergence accelerators. One is the default con verge rice accelerator, effective in speed in g up ri orm ally... 

The rate constants for the catalysed Diels-Alder reaction of 2.4g with 2.5 (Table 2.3) demonstrate that the presence of the ionic group in the dienophile does not diminish the accelerating effect of water on the catalysed reaction. Comparison of these rate constants with those for the nonionic dienophiles even seems to indicate a modest extra aqueous rate enhancement of the reaction of 2.4g. It is important to note here that no detailed information has been obtained about the exact structure of the catalytically active species in the oiganic solvents. For example, ion pairing is likely to occur in the organic solvents. 

Modem real time instmmental methods permit analyses of unstable transient species and the free-radical intermediates as well. These methods have gready expanded the scope and power of VPO studies, but important basic questions remain unresolved. Another complication is the role of surface. Peroxide decompositions and radical termination reactions can occur on a surface so that, depending on circumstances, surfaces can have either an inhibiting or accelerating effect. Each surface has varying amounts of adventitious contaminants and also accumulates deposits during reaction. Thus no two surfaces are exactly alike and each changes with time. 

The classical experiment tracks the off-gas composition as a function of temperature at fixed residence time and oxidant level. Treating feed disappearance as first order, the pre-exponential factor and activation energy, E, in the Arrhenius expression (eq. 35) can be obtained. These studies tend to confirm large activation energies typical of the bond mpture mechanism assumed earlier. However, an accelerating effect of the oxidant is also evident in some results, so that the thermal mpture mechanism probably overestimates the time requirement by as much as several orders of magnitude (39). Measurements at several levels of oxidant concentration are useful for determining how important it is to maintain spatial uniformity of oxidant concentration in the incinerator. 

Succinic anhydride is stabilized against the deteriorative effects of heat by the addition of small amounts (0.5 wt %) of boric acid (27), the presence of which also decreases the formation of the dilactone of gamma ketopimelic acid (28). Compared with argon, CO2 has an inhibiting effect on the thermal decomposition of succinic acid, whereas air has an accelerating effect (29,30). 

The ash content of furnace blacks is normally a few tenths of a percent but in some products may be as high as one percent. The chief sources of ash are the water used to quench the hot black from the reactors during manufacture and for wet pelletizing the black. The hardness of the water, and the amount used determines the ash content of the products. The ash consists principally of the salts and oxides of calcium, magnesium, and sodium and accounts for the basic pH (8—10) commonly found in furnace blacks. In some products potassium, in small amounts, is present in the ash content. Potassium salts are used in most carbon black manufacture to control stmcture and mbber vulcanizate modulus (22). The basic mineral salts and oxides have a slight accelerating effect on the vulcanization reaction in mbber. 

Total pressure drop for horizontal gas/solid flow includes acceleration effects at the entrance to the pipe and fric tional effects beyond the entrance region. A great number of correlations for pressure gradient are available, none of which is applicable to all flow regimes. Govier and Aziz review many of these and provide recommendations on when to use them. 

Description These exchangers are typically a series of stacked helical-coiled tubes connected to manifolds, then inserted into a casing or shell. They have many advantages hke spiral-plate designs, such as avoiding differential expansion problems, acceleration effects of the helical flow increasing the heat transfer coefficient, and compactness of plot area. They are typically selected because of their economical design. 

The accelerating effect of turbulence in alkaline attack on aluminum alloys is well illustrated in this case history. 

Figure 4-68. Acceleration effects under various conditions (1) Vanes fixed (2) Vanes on flow control, no time lag (3) Vanes on flow control, 2 sec lag (4) Vanes fixed until trip, trip moves 5°/sec (5) Same as 4 except moves vanes 10°/sec (6) Same as 4 except moves vanes 15°/sec (7) Same as 4 except moves vanes 20°/sec (8) Vanes on flow control, 2 sec lag, 10°/sec.

The auto-acceleration effect appears most marked with polymers that are insoluble in their monomers. In these circumstances the radical end becomes entrapped in the polymer and termination reactions become very difficult. It has been suggested that, in thermodynamic terms, methyl methacrylate is a relatively poor solvent for poly(methyl methacrylate) because it causes radicals to coil while in solution. The termination reaction is then determined by the rate at which the radical ends come to the surface of the coil and hence become available for mutual termination. 

Conjugated substituents at C-2, C-3, C-4, or C-5 accelerate the rearrangement. Donor substituents at C-2 and C-3 have an accelerating effect. The effect of substituents can be rationalized in terms of the stabilization of the transition state by depicting their effect on two interacting allyl systems. 

A donor substituent, e.g., triraethylsilyloxy, at C-2 has a strongly accelerating effect. 

Carbonates, especially sodium and potassium carbonates, are often added to plywood and LVL mixes to accelerate cure and reduce delaminations and blows. Calcium carbonates do not show a significant accelerating effect. Occasionally esters are used to accelerate plywood mixes [119]. Carbon dioxide also accelerates PF cure [120]. 

These two experiments make a number of important points. An <7-HMP will not react with an ortho position as long as a para reaction site is available. A p-HMP will react with unoccupied ortho position at about half the rate that it reacts with a substituted para position. This suggests that there is something special about the repulsion between the phenolic hydroxyls. Since the pH was only 8, it is clear that there was ample opportunity for a salted 2-HMP to find and react with an unsalted 2-HMP. Both species were present. On this basis, we cannot invoke repulsion of like-charged ions. According to Jones salted species probably react with unsalted species and this is one reason that reaction rate drops rapidly when PF pH gets much above 9.0 [147]. Yet the phenolic hydroxyl appears to be the cause of the reduced reactivity of the ortho position. Unfortunately, Jones did much of his work in a carbonate buffer. He did not realize the pH-dependent accelerating effects of carbonate on PF condensation. 

The condition of the test metal is important. Clean metal samples with uniform finishes are preferred. The accelerating effects of surface defects lead to deceptive results in samples. The ratio of the area of a defect to the total surface area of the metal is much higlier in a sample than in any metal in service. This is an indication of the inaccuracy of tests made on metals with improper finishes. The sample metal should have the same type of heat treatment as the metal to be used in service. Different heat treatments have different effects on corrosion. Heat treatment may improve or reduce the corrosion resistance of a metal in an unpredictable manner. For the purpose of selectivity, a metal stress corrosion test may be performed. General trends of the performance of a material can be obtained from such tests however, it is difficult to reproduce the stress that actually will occur during service. 

These equations can be used when the Mach number is small, and the acceleration effect is ignored. 

The possibility of a radical mechanism is supported by the observation of the accelerating effect of molecular oxygen on the cyclopropanation. Miyano et al. discovered that the addition of dioxygen accelerated the formation of the zinc carbenoid in the Furukawa procedure [24a, b]. The rate of this process was monitored by changes in the concentration of ethyl iodide, the by-product of reagent formation. Comparison of the reaction rate in the presence of oxygen with that in the... 

The use of small amounts of acetic acid is important small amounts have a marked accelerating effect (95) larger amounts promote hydrogenolysis of the benzyl oxygen. 

This gives a target value to the pump supplier that is worst condition. In general, for cold water duty equation (32.16) can be used for the duty flow required. Equation (32.16) is employed for reciprocating and rotary positive displacement machines with allowance made for acceleration effects. 

The formation of molten M0O3 above 815°C results in a catastrophically accelerating effect due to the following factors (a) the liquid oxide flows off the metal surface, (b) the rate of diffusion of oxygen through the liquid phase is high, and (c) the molten oxide can also act as a flux. 

In addition to the boron trifluoride-diethyl ether complex, chlorotrimcthylsilanc also shows a rate accelerating effect on cuprate addition reactions this effect emerges only if tetrahydrofuran is used as the reaction solvent. No significant difference in rate and diastereoselectivity is observed in diethyl ether as reaction solvent when addition of the cuprate, prepared from butyllithium and copper(I) bromide-dimethylsulfide complex, is performed in the presence or absence of chlorotrimethylsilane17. If, however, the reaction is performed in tetrahydrofuran, the reaction rate is accelerated in the presence of chlorotrimethylsilane and the diastereofacial selectivity increases to a ratio of 88 12 17. In contrast to the reaction in diethyl ether, the O-silylated product is predominantly formed in tetrahydrofuran. The alcohol product is only formed to a low extent and showed a diastereomeric ratio of 55 45, which is similar to the result obtained in the absence of chlorotrimethylsilane. This discrepancy indicates that the selective pathway leading to the O-silylated product is totally different and several times faster than the unselective pathway" which leads to the unsilylated alcohol adduct. A slight further increase in the Cram selectivity was achieved when 18-crown-6 was used in order to increase the steric bulk of the reagent. 

Fairly rapid indications of weatherabil-ity are therefore obtainable on samples of known materials that through testing experience over a period of time have general correlations established. There is no artificial substitute for precisely predicting outdoor weatherability on materials with no previous weathering history. Weatherome-ters produce conditions to accelerate effects that would be observed in specimens exposed outdoors. 

Affrossman149 observed the accelerating effects of cation-exchange resins partially neutralized with AgOH toward the hydrolyses of allylacetate. 7r-Electron-binding interactions between Ag+ and the double bond in allylacetate were proposed. 7r-Complex formations of olefine with Cu+ and Ag+ have already been reported150 151. ... 

The accelerating effect of sodium perchlorate on the rate of mercuration by mercuric acetate in acetic acid arises out of the equilibrium... 

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