Stoichiometric condition

Stoichiometry is the composition of the air-fuel mixture required to obtain complete combustion. The stoichiometric ratio, r, is the quotient of the respective masses, and m, of air and fuel arranged in the stoichiometric conditions ... 

But equations (11.41) and (11.42) are mutually consistent only if corresponding Co an isomerization. Where there is a change In number of moles the stoichiometric condition (11.41) cannot be satisfied under iso-baric conditions, so it follows that there must be a pressure gradient in the pellet. 

A third approach is suggested by Hugo s formulation of material balances at the limit of bulk diffusion control, described in Section 11.3. Hugo found expressions for the fluxes by combining the stoichiometric conditions and the Stefan-Maxvell relations, and this led to no inconsistencies since there are only n - 1 independent Stefan-Maxwell relations for the n fluxes. An analogous procedure can be followed when the diffusion is of intermediate type, using the dusty gas model equations in the form (5.10) and (5.11). Equations (5.11), which have the following scalar form ... 

The function of the oxygen sensor and the closed loop fuel metering system is to maintain the air and fuel mixture at the stoichiometric condition as it passes into the engine for combustion ie, there should be no excess air or excess fuel. The main purpose is to permit the TWC catalyst to operate effectively to control HC, CO, and NO emissions. The oxygen sensor is located in the exhaust system ahead of the catalyst so that it is exposed to the exhaust of aU cylinders (see Fig. 4). The sensor analyzes the combustion event after it happens. Therefore, the system is sometimes caUed a closed loop feedback system. There is an inherent time delay in such a system and thus the system is constandy correcting the air/fuel mixture cycles around the stoichiometric control point rather than maintaining a desired air/fuel mixture. 

In order to generate a candidate EAR, one should consider potential raw materials and by-products, satisfaction of stoichiometric conditions, assurance of thermodynamic feasibility, and fulfillment of environmental requirements. These issues can be addressed by employing an optimization formulation to identify an overall reaction that yields the desired product at maximum economic potential while satisfying stoichiometric, thermodynamic, and environmental constraints. For a more detailed description of this optimization program, the reader is referred to Crabtree and El-Halwagi (1994). 

Although lead tetraacetate can attack many polar and nonpolar functions in the steroid molecule, its greatest reactivity is towards vicinal diols. These diols are generally cleaved so rapidly under stoichiometric conditions that other alcohol functions in the molecule need not be protected. Thus lead tetraacetate in acetic acid at room temperature splits the 17a,20-diol group in (9) to yield the 17-ketone (10), the allylic A -3jS-alcohol remaining intact during this oxidation. Since lead tetraacetate is solublein many anhydrous... 

Figure 19.3 Fuel saving versus air preheat temperature (stoichiometric conditions)...

There are several examples of successful dienol epoxidations (Table 9.2). Catalytic SAE conditions are generally better than stoichiometric for reactive substrates (Entry 1), whilst stoichiometric conditions, on the other hand, are useful for less reactive substrates. Small variations in substrate structure can cause large differences in reactivity and product stability pentadienol could be epoxidized in acceptable yield, whereas hexadienol gave a complex mixture of products (Entries 1, 2). 

Reaction orders in alcohol and add were obtained from a study of the first of these reactions under non-stoichiometric conditions. This is not possible for a polyesterification, carried out in an excess of one of the reactants since in this case stoichiometry is required. The orders in acid and alcohol relative to the reaction of 1-dodecanol with dodecanoic add in dodecyl dodecanoate are 2 and 1 respectively which, according to Solomon, corresponds to an Aac2 mechanism. Since the dielectric constant is low, the ions are assumed to be associated as ion pairs ... 

As the large-scale computational fluid dynamics (CFD) simulations often invoke simplifying the kinetics as one-step overall reaction, the extraction of such bulk flame parameter as overall activation energy is especially useful when the CFD calculation with detailed chemistry is not feasible. Based on the experimental results, the deduced overall achvation energies of the three equivalence ratios are shown in Figure 4.1.10a. It can be observed that the variation of with is nonmonotonic and peaks near the stoichiometric condition. 

Comparison of Figure 4.1.10a and b demonsfrafes fhaf despite the quantitative differences in fhe deduced values, bofh fhe extraction methods yield a similar trend in the range of equivalence ratios investigated. The overall activation energy is observed to peak close to the stoichiometric condition and decrease on both the lean and rich sides. In addition, the overall activation energy values for n-heptane/air mixtures are observed to be lower when compared with iso-octane/air mixtures for all equivalence ratios under consideration. This similarity of trend and the differences in absolute values using two different extraction methods are also observed in the numerical computations with the available detailed... 

Trimethylsilyl ylide 95 reacts with PCI3 or AsClj to give respectively the corresponding halophosphorus yhde 96 and the first example known of haloarsanyl ylide 97 [116]. In various stoichiometric conditions the 1 1 condensation of 95 with ASCI3 is realized to give haloarsanyl ylides with either a dimeric structure (diarsenate 98) or trimeric and tetrameric cationic compounds 99 and 100 (Scheme 29). 

Starting from stoichiometric conditions (< = 1) and then proceeding in the lean direction (< < 1), we anticipate that the peak fiame temperature will be reduced gradually. In addition, as the maximum temperature is lowered and the corresponding adiabatic fiame speed of an unstrained a = 0) fiame is reduced, we anticipate that the fiame will move closer to the plane of symmetry. Ultimately, as the fuel to air ratio is lowered below a critical value, radical production in the fiame will be severely restricted and the fiame will extinguish (lean extinction). The arclength continuation procedure will then generate unphysical solutions for additional continuation steps until a maximum value of the... 

The concept of minimum AE and maximum Emw is illustrated with the generalized sequence shown in Scheme 4.7 under stoichiometric conditions with complete recovery of reaction solvents, catalysts, and post-reaction materials. Markush structures are used to show both variable R groups and necessarily invariant atoms. This analysis is useful in studying combinatorial hbraries where a constant scaffold structure is selected and then is decorated with, in principle, an unlimited number of possible R groups. 

Only three steps of the proposed mechanism (Fig. 18.20) could not be carried out individually under stoichiometric conditions. At pH 7 and the potential-dependent part of the catalytic wave (>150 mV vs. NHE), the —30 mV/pH dependence of the turnover frequency was observed for both Ee/Cu and Cu-free (Fe-only) forms of catalysts 2, and therefore it requires two reversible electron transfer steps prior to the turnover-determining step (TDS) and one proton transfer step either prior to the TDS or as the TDS. Under these conditions, the resting state of the catalyst was determined to be ferric-aqua/Cu which was in a rapid equilibrium with the fully reduced ferrous-aqua/Cu form (the Fe - and potentials were measured to be within < 20 mV of each other, as they are in cytochrome c oxidase, resulting in a two-electron redox equilibrium). This first redox equilibrium is biased toward the catalytically inactive fully oxidized state at potentials >0.1 V, and therefore it controls the molar fraction of the catalytically active metalloporphyrin. The fully reduced ferrous-aqua/Cu form is also in a rapid equilibrium with the catalytically active 5-coordinate ferrous porphyrin. As a result of these two equilibria, at 150 mV (vs. NHE), only <0.1%... 

For the sake of simplicity, a 0eO2—Zr02 (70/30) mixed oxide will be now used as material. This mixed oxide has been previously shown to be able to proceed to three-way catalysis, the general concept for N2 formation over a metal cation being the same NO decomposition and oxygen species scavenging, in stoichiometric conditions, by CO as reductant [10,11],... 

In pre-combustion C02 capture, C02 separation occurs prior to fuel combustion and power generation (Figure 5). The fuel reacts at high temperature and pressure with either oxygen or/ and steam under sub-stoichiometric conditions, and thereby a gas stream primarily composed of CO and H2 is obtained. This CO/H2 gas mixture is commonly known as synthesis gas or syngas. 

DHQD-CL or DHQ-CL) was used as the chiral auxiliary.175,176 However, the enantioselectivity observed under catalytic conditions was inferior to that observed under stoichiometric conditions. The addition of triethylammonium acetate, which increases the rate of hydrolysis of the Osvm-glycolate intermediate, improved enantioselectivity. A further improvement in enantioselectivity was brought about by the slow addition of substrates (Scheme 44).177 These results indicated that the hydrolysis of the Osvm-glycolate intermediate (57) was slow under those conditions and (57) underwent low enantioselective dihydroxylation (second cycle). Thus, Sharpless et al. proposed a mechanism of the dihydroxylation including a second cycle (Scheme 45).177 Slow addition reduces the amount of unreacted olefin in the reaction medium and suppresses the... 

Osmium(VIII) tetraoxide (0s04) is an effective reagent for the cis hydroxylation of olefins under stoichiometric conditions as well as in a variety of catalytic variants.213 Under both catalytic and stoichiometric conditions, the critical step is the formation of an osmium(VI) cycloadduct, the formation of which is dramatically accelerated in the presence of amine bases such as pyridine,214 i.e.,... 

Flame temperature. The hydrogen-air flame is hotter than methane-air flame and cooler than gasoline at stoichiometric conditions (2207°C compared to 1917°C for methane and 2307°C for gasoline). 

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