Stoichiometry The relative

Stoichiometry The relative abundance of atoms in a molecule or in a reaction, given in terms of molar quantities. 

Stoichiometry the relative numbers of atomic constituents making up a chemical compound... 

Two-state model, 1 1 Stoichiometry The relative partition function for this model is... 

Both the method of continuous variations and the mole-ratio method rely on an extrapolation of absorbance data collected under conditions in which a linear relationship exists between absorbance and the relative amounts of metal and ligand. When a metal-ligand complex is very weak, a plot of absorbance versus Ay or n-J m may be curved, making it impossible to determine the stoichiometry by extrapolation. In this case the slope ratio may be used. 

A procedure for determining the stoichiometry between two reactants by measuring the relative change in absorbance under conditions when each reactant is the limiting reagent. 

The influence of boron-bonded ligands on the kinetics and mechanistic pathways of hydrolysis of amine boranes has been examined (37,38). The stoichiometry of trimetbyl amine azidoborane [61652-29-7] hydrolysis in acidic solution is given in equation 10. It is suggested that protonation occurs at the azide ligand enabling its departure as the relatively labile HN species. 

When an equilibrium reaction occurs in a vapor-hquid system, the phase compositions depend not only on the relative volatility of the components in the mixture, but also on the consumption (and production) of species. Thus, the condition for azeotropy in a nonreactive system = x, for all i) no longer holds true in a reactive system and must be modified to include reaction stoichiometry ... 

The propensity for iodine to catenate is well illustrated by the numerous polyiodides which crystallize from solutions containing iodide ions and iodine. The symmetrical and unsymmetrical 13 ions (Table 17.15) have already been mentioned as have the I5- and anions and the extended networks of stoichiometry (Fig. 17.12). The stoichiometry of the crystals and the detailed geometry of the polyhalide depend sensitively on the relative concentrations of the components and the nature of the cation. For example, the linear ion may have the following dimensions ... 

Stoichiometry in Reactive Systems. The use of molar units is preferred in chemical process calculations since the stoichiometry of a chemical reaction is always interpreted in terms of the number of molecules or number of moles. A stoichiometric equation is a balanced representation that indicates the relative proportions in which the reactants and products partake in a given reaction. For example, the following stoichiometric equation represents the combustion of propane in oxygen ... 

The relative thicknesses of the fuel and the oxidizer slab are determined by the stoichiometry of the particular propellant formulation. At the surface of the oxidizer slab, the solid oxidizer is assumed to vaporize, producing the gaseous oxidizer decomposition products. At the fuel surface, a similar assumption is made. 

Sometimes we need to know how much product to expect from a reaction, or how much reactant we need to make a desired amount of product. The quantitative aspect of chemical reactions is the part of chemistry called reaction stoichiometry. The key to reaction stoichiometry is the balanced chemical equation. Recall from Section H that a stoichiometric coefficient in a chemical equation tells us the relative amount (number of moles) of a substance that reacts or is produced. Thus, the stoichiometric coefficients in... 

The dominant features which control the stoichiometry of transition-metal complexes relate to the relative sizes of the metal ions and the ligands, rather than the niceties of electronic configuration. You will recall that the structures of simple ionic solids may be predicted with reasonable accuracy on the basis of radius-ratio rules in which the relative ionic sizes of the cations and anions in the lattice determine the structure adopted. Similar effects are important in determining coordination numbers in transition-metal compounds. In short, it is possible to pack more small ligands than large ligands about a metal ion of a given size. 

Ce(IV) sulphate oxidation of NH30H" shows a stoichiometry depending on the relative initial concentrations, but at low [Ce(IV)]/[NH30H ], the conditions for kinetic experiments, a value of 1.0 is realised for A[Ce(IV)]/A[NH30H ] . The reaction orders with respect to oxidant and substrate are both one but 2 is reduced by addition of sulphate ions, indicating 0(804)3 ", the dominant... 

The relative product yields depend on the CHa to Cl ratio on the surface. In the studies reported here, this ratio has been adjusted to 1 1 (consistent with the CHa Cl stoichiometry in CHaCl) on the basis of a Cl(181 eV) C(272 eV) Auger peak ratio of 6.5 which is the same as that measured for physisorbed monolayers of dimethyldichlorosilane. Monolayer coverages of CHa + Cl having 1 1 stoichiometry were obtained by a 20 L exposure from the methyl radical source (approximately sahiration coverage) followed by a 9.5 L dose of CI2. 

It is intriguing to note that this reaction scheme for the reduction of a sulphone to a sulphide leads to the same reaction stoichiometry as proposed originally by Bordwell in 1951. Which of the three reaction pathways predominates will depend on the relative activation barriers for each process in any given molecule. All are known. Process (1) is preferred in somewhat strained cyclic sulphones (equations 22 and 24), process (2) occurs in the strained naphtho[l, 8-hc]thiete 1,1-dioxide, 2, cleavage of which leads to a reasonably stabilized aryl carbanion (equation 29) and process (3) occurs in unstrained sulphones, as outlined in equations (26) to (28). Examples of other nucleophiles attacking strained sulphones are in fact known. For instance, the very strained sulphone, 2, is cleaved by hydride from LAH, by methyllithium in ether at 20°, by sodium hydroxide in refluxing aqueous dioxane, and by lithium anilide in ether/THF at room temperature. In each case, the product resulted from a nucleophilic attack at the sulphonyl sulphur atom. Other examples of this process include the attack of hydroxide ion on highly strained thiirene S, S-dioxides , and an attack on norbornadienyl sulphone by methyllithium in ice-cold THF . ... 

Densification is also influenced by the presence of supporting electrolyte. As shown in the last line of Table II, the relative densification in acidified cupric sulfate is less than that in binary cupric sulfate solution. In the case of the supported redox reaction, that is, in the presence of KOH or NaOH, the migration effect makes the density difference larger than that expected from overall reaction stoichiometry. 

Are Side Reactions Important What is the Stoichiometry of the Reaction When a mixture of various species is present in a reaction vessel, one often has to worry about the possibility that several reactions, and not just a single reaction, may occur. If one is trying to study one particular reaction, side reactions complicate chemical analysis of the reaction mixture and mathematical analysis of the raw data. The stoichiometry of the reaction involved and the relative importance of the side reactions must be determined by qualitative and quantitative anal-lysis of the products of the reaction at various times. If one is to observe the growth and decay of intermediate products in series reactions, measurements must be made on the reaction system before the reaction goes to completion. 

At least for ethylene hydrogenation, catalysis appears to be simpler over oxides than over metals. Even if we were to assume that Eqs. (1) and (2) told the whole story, this would be true. In these terms over oxides the hydrocarbon surface species in the addition of deuterium to ethylene would be limited to C2H4 and C2H4D, whereas over metals a multiplicity of species of the form CzH D and CsHs-jD, would be expected. Adsorption (18) and IR studies (19) reveal that even with ethylene alone, metals are complex. When a metal surface is exposed to ethylene, selfhydrogenation and dimerization occur. These are surface reactions, not catalysis in other words, the extent of these reactions is determined by the amount of surface available as a reactant. The over-all result is that a metal surface exposed to an olefin forms a variety of carbonaceous species of variable stoichiometry. The presence of this variety of relatively inert species confounds attempts to use physical techniques such as IR to char-... 

---