Hardness and softness

There is an alternative view of acid-base reactions that relies on the Lewis acid-base definition but has been used to classify a wide range of organic reaction types. Cations are classified as Lewis acids, anions are Lewis bases and salts are viewed as acid-base complexes. When one writes the normal acid-base equation, certain conventions are observed. 

For example, if the acid (A) is chromic acid, there is a different basicity order than if A is cuprous ion. Usually, the simple equation shown above is inadequate and requires additional terms 

The Edward s equation - (Eqn. 2.2) can he of value for determining the relative strength of Lewis acids and is written as 

There are obviously many acids, but the proton (H+) and an alkyl mercuric ion (RHg ) have roughly opposite affinities for binding bases. The values of the parameters for the Edward s equation for H+ are a = 

and p = 2.000 and for MeHg the values are a = 5.786 and p = -0.031. The reactions of these two acids with Lewis bases define the relative strengths of the Lewis bases, which gives rise to two observations. 

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Figure C3.3.7. In the upper half of the figure are shown typical measured Doppler profiles for molecules scattered into the (OO O J= 72) or (OO l J = 17) states of CO2 by collisions with hot pyrazine having an energy of 40 640 cm In the lower half of the figure is shown a typical intennolecular potential identifying the hard and soft collision regimes and the kind of energy transfer they effect.

Analogous to the classification of Lewis acids and bases in hard and soft species, Ahrland et al. have su ested a division of donors and acceptors into classes a and 6. See Ahrland, S. Chatt, J. Davies, N.R. Quart. Rev. 1958, 77, 265... 

Ambident reactivity of A-4-thiazoline-2-thione has been discussed (101) in terms of the Hard and Soft Acids and Bases classification (199) and the Klopman-Hudson approach (200). 

T. L. Ho, Hard and Soft Acids and Bases Principle in Organic Chemisty, Academic Press, New York, 1977. 

Soft-wheat flours are sold for general family use, as biscuit or cake flours, and for the commercial production of crackers, pretzels, cakes, cookies, and pastry. The protein in soft wheat flour mns from 7 to 10%. There are differences in appearance, texture, and absorption capacity between hard- and soft-wheat flour subjected to the same milling procedures. Hard-wheat flour falls into separate particles if shaken in the hand whereas, soft-wheat flour tends to clump and hold its shape if pressed together. Hard-wheat flour feels slightly coarse and granular when mbbed between the fingers soft-wheat flour feels soft and smooth. Hard-wheat flour absorbs more Hquid than does soft-wheat flour. Consequently, many recipes recommend a variable measure of either flour or Hquid to achieve a desired consistency. 

Fig. 3. An overview of atomistic mechanisms involved in electroceramic components and the corresponding uses (a) ferroelectric domains capacitors and piezoelectrics, PTC thermistors (b) electronic conduction NTC thermistor (c) insulators and substrates (d) surface conduction humidity sensors (e) ferrimagnetic domains ferrite hard and soft magnets, magnetic tape (f) metal—semiconductor transition critical temperature NTC thermistor (g) ionic conduction gas sensors and batteries and (h) grain boundary phenomena varistors, boundary layer capacitors, PTC thermistors.

Bases of low polarizabiUty such as fluoride and the oxygen donors are termed hard bases. The corresponding class a cations are called hard acids the class b acids and the polarizable bases are termed soft acids and soft bases, respectively. The general rule that hard prefers hard and soft prefers soft prevails. A classification is given in Table 3. Whereas the divisions are arbitrary, the trends are important. Attempts to provide quantitative gradations of "hardness and softness" have appeared (14). Another generaUty is the usual increase in stabiUty constants for divalent 3t5 ions that occurs across the row of the Periodic Table through copper and then decreases for zinc (15). 

Impression plasters are used to obtain an impression (or negative) of the hard and soft tissues of the mouth. The plaster slurry is placed in a tray, inserted into the mouth, pressed in place against the area in question, and held stiU until it hardens. 

Elastomer Impression Materials. Dentistry requires impression materials that are easily handled and accurately register or reproduce the dimensions, surface details, and interrelationship of hard and soft oral tissues. Elexible, elastomeric materials are especially needed to register intraoral tooth stmctures that have undercuts. The flexibility of these elastomers allows their facile removal from undercut areas while their elasticity restores them to their original shape and size. 

Thermoplastic elastomers that are hard polymer/elastomer combinations are often not truly synthesized. Instead, the two polymers that form the hard and soft phases are intimately mixed on high shear equipment. 

Performance The dry pan is usebil for crushing medium-hard and soft materials such as clays, shales, cinders, and soft minerals such as barites. Materials fed should normally be 7.5 cm (3 in) or smaller, and a produc t able to pass No. 4 to No. 16 sieves can be dehvered, depending on the hardness of the material. 

One partieular form of thermoplastic polyurethane elastomers is the elastic fibre known as spandex fibre. Like the usual thermoplastic rubbers these materials consist of hard and soft segments but to qualify for the term spandex by the US Federal Trade Commission the polymer used should contain at least 85% of segmented polyurethane. The first commercial material of this type was introduced by Du Pont in 1958 (Lycra). Several other similar materials have since been introduced including Dorlastan (Bayer), Spanzelle (Courtaulds) and Vyrene (US Rubber). 

Qualitative relationship between orbital energies, hardness, and softness... 

R. G. Pearson, J. Am. Chem. Soc. 85 3533 (1963) T. L. Ho, Hard and Soft Acids and Bases in Organic Chemistry, Academic Press, New York, 1977 W. B. Jensen, The Lewis Acid-Base Concept, Wiley-Interscience, New York, 1980, Chapter 8. 

DFT turns out to be well suited to quantitative expression of some of the qualitative concepts introduced in Section 1.2, such as electronegativity, hardness, and softness. The pnnciple of maximum hardness (p. 22) can be denved as a consequence of DFT, as can the concepts of hardness and softness. ... 

The strength of the complexation is a function of both the donor atom and the metal ion. The solvent medium is also an important factor because solvent molecules that are potential electron donors can compete for the Lewis acid. Qualitative predictions about the strength of donor-acceptor complexation can be made on the basis of the hard-soft-acid-base concept (see Section 1.2.3). The better matched the donor and acceptor, the stronger is the complexation. Scheme 4.3 gives an ordering of hardness and softness for some neutral and ionic Lewis acids and bases. 

Sometimes discussed in terms of hard and soft acids and bases. 

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