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1.4 Acids and Bases The Arrhenius concept was of basic importance because it permitted quantitative treatment of a number of acid-base processes in aqueous solutions, i.e. the behaviour of acids, bases, their salts and mixtures of these substances in aqueous solutions. Nonetheless, when more experimental material was collected, particularly on reaction rates of acid-base catalysed processes, an increasing number of facts was found that was not clearly interpretable on the basis of the Arrhenius theory (e.g. in anhydrous acetone NH3 reacts with acids in the absence of OH~ and without the formation of water). It gradually became clear that a more general theory was needed. Such a theory was developed in 1923 by J. N. Br0nsted and, independently, by T. M. Lowry. 1.4.1 Definitions The generalization was based on the introduction of the concept of donor-acceptor pairs into the theory of acids and bases; this is a fundamental concept in the general interpretation of chemical reactivity. In the same way as a redox reaction depends on the exchange of electrons between the two species forming the redox system, reactions in an acid-base system also depend on the exchange of a chemically simple species hydrogen cations, i.e. protons. Such a reaction is thus termed protolytic. This approach leads to the following definitions: An acid HA is a substance capable of splitting off a proton: A base B is a substance capable of bonding a proton: B + H + ->BH + Substances capable of splitting off a proton, i.e. proton donors, are termed protogenic and, on the other hand, substances accepting protons, i.e. proton



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for those two subnets falls at the 27th bit marker. The figure does not show this second split, but you can do this exercise yourself by moving the common line to the right 1 bit and seeing that both 10.15.1.32/28 and 10.15.1.48/28 can be summarized as a single aggregate, 10.15.1.32/27.





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46 accceptors, are protophilic Some substances can exhibit both of these properties, ie can either accept or donate a proton, and are termed amphiprotic The pairs HA A and B HB differ only by the presence or absence of a proton (in the same way as the oxidized form differs from the reduced form in a redox system only by the presence or absence of an electron) The substances HA and A~ or B and BH + form a conjugate pair A strong acid is conjugate with a weak base and a strong base is conjugate with a weak acid An important characteristic of the definitions should be noted: no mention is made of the charge of species HA, A, B and HB Acids and bases can be either electrically neutral molecules or ions.

Figure 5.27 We would like to use common line /25, but there are bit patterns for subnets that are not part of the original six subnets. This means that we cannot aggregate all of these subnets into a single CIDR advertisement.

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6.4 In many venues, uncluttered or smooth backgrounds are hard to nd. I decided to use a camera angle that diminished the background and used the striped track lines to frame my subject, long-distance runner Ian Reschke. Taken at ISO 500, f/2.8, 1/4000 second with a 15.2mm lens setting.

As free proton cannot exist alone in solution, reactions in which a proton is split off from an acid to form a conjugate base cannot occur in an isolated system (in a homogeneous solution although this is possible in electrolysis (Section 571)) The homogeneous solution must contain another base B n that accepts a proton from the acid HAr (acid HAX is, of course, not conjugate with base B n ) It will be seen that this second base can even be the solvent molecule, provided it has protophilic properties Acid-base reactions thus depend on the exchange of a proton between an acid and a base that are not mutually conjugate^ HAl + B n ^ Ax + HB n (141) This scheme describes, in a uniform manner, all the reactions considered in the classical (Arrhenius) theory as different processes, giving them different names.

Expected Common Line (/25) Common bit pattern 10.15.1.32/28 10.15.1.48/28 10.15.1.64/28 10.15.1.80/28 10.15.1.96/28 10.15.1.112/28 00001010 . 00001111 . 00000001 . 0 010 0000 00001010 . 00001111 . 00000001 . 0 011 0000 00001010 . 00001111 . 00000001 . 0 100 0000 00001010 . 00001111 . 00000001 . 0 101 0000 00001010 . 00001111 . 00000001 . 0 110 0000 00001010 . 00001111 . 00000001 . 0 111 0000 00 00 0000 00 01 0000 00 10 0000 00 11 0000 01 00 0000 01 01 0000 01 10 0000 01 11 0000 Need to split Into 2 sets at This boundary Network Line (/28) Real Common Line (/26)

They include, for example, HC1 + NH3-> CP + NH 4 + HC1 + H2O-> C\~ + H 3 O + H2O + N H 3 ^ OH" + NH 4 + H2O + H2O -> OH" + H 3 O + H 3 O + + OH" -* H2O + H2O NH4+ + H2O -> NH3 + H 3 O + H2O + CH3COO~ -> OH~ + CH3COOH 142 Solvents and self-ionization To begin with, molecular solvents with high permittivities will be considered Classification of solvents on the basis of their permittivities agrees roughly with classification as polar and non-polar, and the borderline between these two categories is usually considered to be a relative dielectric constant of 30-40 Below this value ion pairs are markedly formed From.

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f As the acid-base equilibrium is dynamic the reaction HA + A*~ < * A~ + HA*, where HA = and HA* are identical, unceasingly takes place at a high rate but has no influence on the equilibrium properties of the system (cf. p. 99).

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