Base stoichiometry

The quantitative aspects of acid-base chemistry obey the principles Introduced earlier in this chapter. The common acid-base reactions that are important in general chemistry take place in aqueous solution, so acid-base stoichiometry uses molarities and volumes extensively. Example Illustrates the essential features of aqueous acid-base stoichiometry. 

Hoppe, A., Christensen, K. and Swanson, J. A. (2002). Fluorescence resonance energy transfer-based stoichiometry in living cells. Biophys. J. 83, 3652-64. 

Ion-protein combinations which do not specifically involve dissociable groups shed no light on acid-base stoichiometry. The number of sites... 

A. Hoppe, K. Christensen, J.A. Swanson, Fluorescence Resonance Energy Transfer-Based Stoichiometry in Living Cells, Biophys. J. 83, 3,652 (2002)... 

In contrast to boron-centered Lewis acids, tin and titanium derivatives prefer a 1 2 (acid base) stoichiometry in complexation with carbonyls. and H NMR spectra of an equimolar solution of SnCU and 4-f-butylbenzaldehyde showed signds only for free ligand and a 1 2 (acid base) complex over a wide temperature range. Only with excesses of SnCU was any 1 1 adduct observed and even in the presence of 10 equiv. of Lewis acid, only 25% of the 1 1 complex could be detected. Intermolecular exchange in this case was shown to be slow below -40 C and no synr-anti isomerization could be detected. 

Typically important factors Reagent stoichiometry Base stoichiometry Catalyst loading Addition rate (reagent/base) Concentration Reagent identity Base identity Catalyst identity Order of addition Solvent identity... 

Techniques responding to the absolute amount of analyte are called total analysis techniques. Historically, most early analytical methods used total analysis techniques, hence they are often referred to as classical techniques. Mass, volume, and charge are the most common signals for total analysis techniques, and the corresponding techniques are gravimetry (Chapter 8), titrimetry (Chapter 9), and coulometry (Chapter 11). With a few exceptions, the signal in a total analysis technique results from one or more chemical reactions involving the analyte. These reactions may involve any combination of precipitation, acid-base, complexation, or redox chemistry. The stoichiometry of each reaction, however, must be known to solve equation 3.1 for the moles of analyte. 

The accuracy of a standardization depends on the quality of the reagents and glassware used to prepare standards. For example, in an acid-base titration, the amount of analyte is related to the absolute amount of titrant used in the analysis by the stoichiometry of the chemical reaction between the analyte and the titrant. The amount of titrant used is the product of the signal (which is the volume of titrant) and the titrant s concentration. Thus, the accuracy of a titrimetric analysis can be no better than the accuracy to which the titrant s concentration is known. 

Avoiding Impurities Precipitation gravimetry is based on a known stoichiometry between the analyte s mass and the mass of a precipitate. It follows, therefore, that the precipitate must be free from impurities. Since precipitation typically occurs in a solution rich in dissolved solids, the initial precipitate is often impure. Any impurities present in the precipitate s matrix must be removed before obtaining its weight. 

Quantitative Calculations In acid-base titrimetry the quantitative relationship between the analyte and the titrant is determined by the stoichiometry of the relevant reactions. As outlined in Section 2C, stoichiometric calculations may be simplified by focusing on appropriate conservation principles. In an acid-base reaction the number of protons transferred between the acid and base is conserved thus... 

In an indirect analysis the analyte participates in one or more preliminary reactions that produce or consume acid or base. Despite the additional complexity, the stoichiometry between the analyte and the amount of acid or base produced or consumed may be established by applying the conservation principles outlined in Section 2C. Example 9.3 illustrates the application of an indirect analysis in which an acid is produced. 

Where Is the Equivalence Point In discussing acid-base titrations and com-plexometric titrations, we noted that the equivalence point is almost identical with the inflection point located in the sharply rising part of the titration curve. If you look back at Figures 9.8 and 9.28, you will see that for acid-base and com-plexometric titrations the inflection point is also in the middle of the titration curve s sharp rise (we call this a symmetrical equivalence point). This makes it relatively easy to find the equivalence point when you sketch these titration curves. When the stoichiometry of a redox titration is symmetrical (one mole analyte per mole of titrant), then the equivalence point also is symmetrical. If the stoichiometry is not symmetrical, then the equivalence point will lie closer to the top or bottom of the titration curve s sharp rise. In this case the equivalence point is said to be asymmetrical. Example 9.12 shows how to calculate the equivalence point potential in this situation. 

Grades, Quality Control. Fluorspar is marketed ia several grades metallurgical fluorspar (metspar) is sold as gravel, lump, or briquettes. The minimum acceptable assay is 60% effective calcium fluoride. The effective value is determined by subtracting from the contained calcium fluoride 2.5% for every percent of Si02 found ia the complete analysis apparently based on the following stoichiometry (1) ... 

Silica. Sihca, which has the greatest impact on yield losses, reacts with HF and is discharged from the manufacturing process as H2SiFg. Yield losses can be calculated based on the chemical stoichiometry ... 

Coproductioa of ammonium sulfate is a disadvantage of the formamide route, and it has largely been supplanted by processes based on the direct hydrolysis of methyl formate. If the methanol is recycled to the carbonylation step the stoichiometry corresponds to the production of formic acid by hydration of carbon monoxide, a reaction which is too thermodynamicaHy unfavorable to be carried out directly on an iadustrial scale. 

Butane-Based Fixed-Bed Process Technology. Maleic anhydride is produced by reaction of butane with oxygen using the vanadium phosphoms oxide heterogeneous catalyst discussed earlier. The butane oxidation reaction to produce maleic anhydride is very exothermic. The main reaction by-products are carbon monoxide and carbon dioxide. Stoichiometries and heats of reaction for the three principal reactions are as follows ... 

Aldehydes. Alkyleneamines react exothermically with ahphatic aldehydes. The products depend on stoichiometry, reaction conditions, and stmcture of the alkyleneamine. Reactions of aldehydes with ethyleneamines like EDA or DETA give mono- and disubstituted imidazohdines via cyclization of the intermediate Schiff base (20). 

The often fast binding step of the inhibitor I to the enzyme E, forming the enzyme inhibitor complex E-I, is followed by a rate-determining inactivation step to form a covalent bond. The evaluation of affinity labels is based on the fulfillment of the following criteria (/) irreversible, active site-directed inactivation of the enzyme upon the formation of a stable covalent linkage with the activated form of the inhibitor, (2) time- and concentration-dependent inactivation showing saturation kinetics, and (3) a binding stoichiometry of 1 1 of inhibitor to the enzyme s active site (34). 

Synthesis Ga.s, Since petroleum prices rose abmpdy in 1974, the production of ethanol from synthesis gas, a mixture of carbon monoxide and hydrogen, has received considerable attention. The use of synthesis gas as a base raw material has the same drawback as fermentation technology low yields limited by stoichiometry. 

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