Acid-base complexes

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. 

Thus far we have examined titrimetric methods based on acid-base, complexation, and redox reactions. A reaction in which the analyte and titrant form an insoluble precipitate also can form the basis for a titration. We call this type of titration a precipitation titration. 

Titrimetric methods have been developed using acid-base, complexation, redox, and precipitation reactions. Acid-base titrations use a strong acid or strong base as a titrant. The most common titrant for a complexation titration is EDTA. Because of their... 

The following experiments may he used to illustrate the application of titrimetry to quantitative, qtmlitative, or characterization problems. Experiments are grouped into four categories based on the type of reaction (acid-base, complexation, redox, and precipitation). A brief description is included with each experiment providing details such as the type of sample analyzed, the method for locating end points, or the analysis of data. Additional experiments emphasizing potentiometric electrodes are found in Chapter 11. 

Potcntiomctric Titrations In Chapter 9 we noted that one method for determining the equivalence point of an acid-base titration is to follow the change in pH with a pH electrode. The potentiometric determination of equivalence points is feasible for acid-base, complexation, redox, and precipitation titrations, as well as for titrations in aqueous and nonaqueous solvents. Acid-base, complexation, and precipitation potentiometric titrations are usually monitored with an ion-selective electrode that is selective for the analyte, although an electrode that is selective for the titrant or a reaction product also can be used. A redox electrode, such as a Pt wire, and a reference electrode are used for potentiometric redox titrations. More details about potentiometric titrations are found in Chapter 9. 

Representative Examples of Coulometric Titrations Using Acid-Base, Complexation, and Precipitation Reactions... 

This experiment describes the use of coated graphite electrodes for the potentiometric monitoring of precipitation, acid-base, complexation, and redox titrations. 

Neutral compounds such as boron trifluoride and aluminum chloride form Lewis acid-base complexes by accepting an electron pair from the donor molecule. The same functional groups that act as lone-pair donors to metal cations can form complexes with boron trifluoride, aluminum chloride, and related compounds. 

The authors claim that these associations, which are destroyed in fixed compounds, play an important role in the calculation of Ty.The cases of 1,2,4-triazole-5-thiones 74 [97SA(A)699] and of pyridone dimers 15a-15a and 15a-15b were also studied [96MI(13)65]. (3) The recording of IR spectra in solution at different temperatures to determine the effect of the temperature on Kj-, for instance, in pyrazolinones [83JPR(325)238] and in cytosine-guanine base pairs [92MI(9)881]. (4) The determination of the equilibrium 2-aminopyridine/acetic acid 2-aminopyridinium acetate (see Section III.E) in the acid-base complex was carried out by IR (97NKK100). 

A Grignard reaction begins with an acid-base complexation of Vfg2+ to the carbonyl oxygen atom of the aldehyde or ketone, thereby making the carbonyl group a better electrophile. Nucleophilic addition of R then produces a tetrahedral magnesium alkoxide intermediate, and protonation by addition of water... 

Another drawback to the use of amino-substituted benzenes in electrophilic aromatic substitution reactions is that Friedel-Crafts reactions are not successful (Section 16.3). The amino group forms an acid-base complex with the AICI3 catalyst, which prevents further reaction from occurring. Both drawbacks can be overcome, however, b3 carrying out electrophilic aromatic substitution reactions on the corresponding amide rather than on the free amine. 

Those related to the nucleophilic character of the active oxygen atom. The resulting acid-base reactions are only dangerous if the acid-base complex obtained is unstable. 

The same happens with the same ether and titanium or zirconium tetrachloride. When the acid leads to an acid-base complex, which is particularly unstable ... 

In the same way, the following scheme represents the preparation of two acid-base complexes of 1,4-dioxan, which detonates when it is stored at 20°C (in the case of the complex with SO3) or in the dry state (with the aluminium derivative) ... 

Amine basicity is related to the presence of a lone pair of electrons on the nitrogen atom. Usually the interaction of an amine with an acid is not dangerous. There can be an accident when the acid-base complex formed is unstable or the operating mode is not correct. 

Closely related to, but distinct from, the anionic boron and aluminum hydrides are the neutral boron (borane, BH3) and aluminum (alane, A1H3) hydrides. These molecules also contain hydrogen that can be transferred as hydride. Borane and alane differ from the anionic hydrides in being electrophilic species by virtue of the vacant p orbital and are Lewis acids. Reduction by these molecules occurs by an intramolecular hydride transfer in a Lewis acid-base complex of the reactant and reductant. 

Reduction of ketones to triphenylsilyl ethers is effected by the unique Lewis acid perfluorotriphenylborane. Mechanistic and kinetic studies have provided considerable insight into the mechanism of this reaction.186 The salient conclusion is that the hydride is delivered from a borohydride ion, not directly from the silane. Although the borane forms a Lewis acid-base complex with the ketone, its key function is in delivery of the hydride. 

When silylenes are generated photochemically in hydrocarbon matrices in the presence of electron-pair donors, they may form Lewis acid-base complexes that act as intermediates in the silylene dimerization to disilenes.3233 In a typical example, Mes2Si(SiMe3)2 was photolyzed in 3-meth-ylpentane (3-MP) matrix containing 5% of 2-methyltetrahydrofuran. At 77 K, dimesitylsilylene (Amax 577 nm) was formed. When the matrix was... 

Ammonia reacts with boron trichloride to form a molecule called an adduct or Lewis acid base complex in which the lone pair on the ammonia molecule is shared with the boron atom to form a covalent bond and completing an octet on boron (Figure 1.16) ... 

We should note that the formation of this bond confers formal charges on the B and N atoms. In this bond and many similar Lewis acid-base complexes both the electrons forming the bond come from the same atom rather than from different atoms, as in the formation of a bond between two chlorine atoms. This type of bond is often called a donor-acceptor bond, a dative bond, or a coordinate bond, and is sometimes given a special symbol—an arrow denoting the direction in which the electron pair is donated ... 

Figure 1.16 The ammonia-boron trifluoride donor-acceptor complex (a) donor Lewis base, (b) acceptor Lewis acid, (c) the donor-acceptor or Lewis acid-base complex.

Sternberg et al. (7) showed that the presence of asphaltenes in coal-derived oils caused a marked increase in the viscosity. This group also showed that these asphaltenes were acid-base complexes and that hydrogen bonding occurs between the acidic and basic components of asphaltenes (9, 10). Recent work (J3, 11) on coal liquefaction bottoms has shown the importance of hydrogen bonding on the viscosity of coal liquids. 

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