Practical Stoichiometry

The negative sign associated with w indicates that less oxygen from air is needed for complete oxidation because atoms of oxygen already exist in the fuel itself. In most situations it is convenient to normalize the actual mixture composition to the stoichiometric mixture composition for that fuel-oxidizer system. The normalization yields a dimensionless number whose magnitude tells us how far the mixture composition has deviated from stoichiometric conditions. The most 

With this definition, mixtures with 0 1 are said to be fuel-lean while those with 0 1 are said to be fuel-rich. Two ofher dimensionless ratios that are commonly used to specify the composition of a combustible mixture relative to the stoichiometric composition are the percent theoretical air and percent excess air. These are defined respectively as 100/0 and 100(1/0- 1). Thus, a mixture that has O = 0.8 can also be said to contain 125 percent theoretical air or 25 percent excess air. 

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We have already discussed under practical stoichiometry how the air requirements can be estimated based on the fuel composition (ultimate analysis). The primary and secondary air requirements for combustion of pulverized coal or coke are best estimated by mass and heat balance at the mill. In Appendix 6A we show a calculation taken from Musto (1997) for the primary and secondary air required for coal pulverizer with 4.5 metric ton per hour (10,0(X)lb/hr) coal feed rate at initial moisture of 15 percent which is required to be ground and dried to 2 percent with a 200 HP mill. In order to estimate the actual primary and secondary air, one has to make some estimation of the evaporation rate, the amount of gas entering the coal mill, and the bleed air required so that the quantity of air that should be vented from the hood off-take can be properly estimated. It shows that for a take-off gas temperature of 315°C (600° F) and vent gas temperature of 76°C (170°F) and allowing ambient air infiltration of 10 percent at 15°C (60°F) the primary air will be about 22 percent of stoichiometric air and 21 percent of total air. The remaining air (about 79 percent) will be the secondary air. With this information we can size a burner using a burner pipe diameter based on a Craya-Curtet parameter of choice bearing in mind the conditions that ensure the desired jet recirculation patterns described in Chapter 3. 

In practice, for motors, turbines or furnaces, the conditions of combustion are frequently far from those corresponding to stoichiometry and are characterized either by an excess or by an insufficiency of fuel with respect to oxygen. The composition of the fuel-air mixture is expressed by the equivalence ratio, (p, defined by the relation / 5 r)... 

The quantity coming from air is practically invariant and corresponds to a level approaching 130 mg/Nm. Nitrogen present in the fuel is distributed as about 40% in the form of NO and 60% as N2. With 0.3% total nitrogen in the fuel, one would have, according to stoichiometry, 850 mg/Nm of NO in the exhaust vapors. Using the above hypothesis, the quantity of NO produced would be (//-U... 

In principle, Chen, given the flux relations there is no difficulty in constructing differencial equations to describe the behavior of a catalyst pellet in steady or unsteady states. In practice, however, this simple procedure is obstructed by the implicit nature of the flux relations, since an explicit solution of usefully compact form is obtainable only for binary mixtures- In steady states this impasse is avoided by using certain, relations between Che flux vectors which are associated with the stoichiometry of Che chemical reaction or reactions taking place in the pellet, and the major part of Chapter 11 is concerned with the derivation, application and limitations of these stoichiometric relations. Fortunately they permit practicable solution procedures to be constructed regardless of the number of substances in the reaction mixture, provided there are only one or two stoichiomeCrically independent chemical reactions. 

Excess alkylating reagent is required if the tetraorganotin is desired as the exclusive product. In commercial practice, the stoichiometry is kept at or below 4 1, since the cmde product is usually redistributed to lower organotin chlorides in a subsequent step and an ether is used as the solvent (86). The use of diethyl ether in the Grignard reaction has been generally replaced with tetrahydrofuran. 

The model assumes that liquid evaporation is always the rate controlling step. At some point the model must fail, since as droplet size approaches zero the predicted MIE approaches zero rather than the MIE of the vapor in air. In practice, droplets having diameters less than 10-40 /rm completely evaporate ahead of the flame and burn as vapor (5-1.3). The model also predicts that the MIE continuously decreases as equivalence ratio is increased, although as discussed above, combustion around droplets is not restrained by the overall stoichiometry and naturally predominates at the stoichiometric concentration. It is recommended that the model be applied only to droplet diameters above about 20/rm and equivalence ratios less than about one. 

The general topic of this chapter is stoichiometry (stoy-key-OM-e-tree), the study of mass relations in chemistry. Whether dealing with atomic masses (Section 3.1), molar masses (Section 3.2), chemical formulas (Section 3.3), or chemical reactions (Section 3.4), you will be answering some very practical questions that ask how much or how many—." For example—... 

Chemistry is a quantitative science. This means that a chemist wishes to know more than the qualitative fact that a reaction occurs. He must answer questions beginning How much. . . The quantities may be expressed in grams, volumes, concentrations, percentage composition, or a host of other practical units. Ultimately, however, the understanding of chemistry requires that amounts be related quantitatively to balanced chemical reactions. The study of the quantitative relationships implied by a chemical reaction is called stoichiometry. 

Stoichiometry has important practical applications, such as predicting how much product can be formed in a reaction. For example, in the space shuttle fuel cell, oxygen reacts with hydrogen to produce water, which is used for life support (Fig. L.l). Let s look at the calculation space shuttle engineers would have to do to find out how much water is formed when 0.25 mol 02 reacts with hydrogen gas. 

Intercalation from solutions in nonaqueous solvents (S21). This method may suffer from the drawback that final stoichiometries may not correspond to equilibrium conditions, because of partial leaching out of metal halide. For this reason, some chlorides can be intercalated only from solvents in which they have limited solubility iLS). It has often been the practice to wash intercalates with solvents to remove the excess of intercalant this may lead to stoichiometries lower than the original ones. The two-ampoule method may, therefore, be preferable (H24). 

In the general case of a piston flow reactor, one must solve a fairly small set of simultaneous, ordinary differential equations. The minimum set (of one) arises for a single, isothermal reaction. In principle, one extra equation must be added for each additional reaction. In practice, numerical solutions are somewhat easier to implement if a separate equation is written for each reactive component. This ensures that the stoichiometry is correct and keeps the physics and chemistry of the problem rather more transparent than when the reaction coordinate method is used to obtain the smallest possible set of differential... 

We begin this chapter with a discussion of the principles of redox reactions, including redox stoichiometry. Then we introduce the principles of electrochemishy. Practical examples of redox chemistry, including corrosion, batteries, and metallurgy, appear throughout the chapter. 

At present, intercalation compounds are used widely in various electrochemical devices (batteries, fuel cells, electrochromic devices, etc.). At the same time, many fundamental problems in this field do not yet have an explanation (e.g., the influence of ion solvation, the influence of defects in the host structure and/or in the host stoichiometry on the kinetic and thermodynamic properties of intercalation compounds). Optimization of the host stoichiometry of high-voltage intercalation compounds into oxide host materials is of prime importance for their practical application. Intercalation processes into organic polymer host materials are discussed in Chapter 26. 

In practice there is a need for characterization of the dispersion, if it were only to estimate the efficiency of the catalytically active component. This can be done by chemisorption of a gas that adsorbs at the surface of the metal particles. H2, CO, O2, and N2O are applied most often. For the calculation of the dispersion it is of paramount importance that the stoichiometry of the adsorption reaction is known and that the reaction is limited to the surface. 

Stoichiometry (from the Greek stoikeion—element) is the practical application of the law of multiple proportions. The stoichiometric equation for a chemical reaction states unambiguously the number of molecules of the reactants and products that take part from which the quantities can be calculated. The equation must balance. 

Practically all coals can be converted to the desired stoichiometry at short time. 

It is always wise to calibrate physical methods of analysis using mixtures of known composition under conditions that approximate as closely as practicable those prevailing in the reaction system. This procedure is recommended because side reactions can introduce large errors and because some unforeseen complication may invalidate the results obtained with the technique. For example, in spectrophotometric studies of reaction kinetics, the absorbance that one measures can be grossly distorted by the presence of small amounts of highly colored absorbing impurities or by-products. For this reason, when one uses indirect physical methods in kinetic studies, it is essential to verify the stoichiometry of the reaction to ensure that the products of the reaction and their relative mole numbers are known with certainty. For the same reason it is recommended that more than one physical method of analysis be used in detailed kinetic studies. 

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