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The value of kT\nK'n differs from this expression by the electric work necessary for removal of a further proton from the field of an n-fold ionized molecule If the electric charge of an rt-times ionized molecule is AG^, this work is equal to dG^/dn Then we have -kT In K'n = -kT In K'Q + ~ (1519) dn Except at the first stage in neutralization titration, ie for small values of n, all the molecules in solution are found experimentally to be ionized to the same degree a = n/N Then.

N=N (K 33 C Ch 43 C I)

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QrCode . Net - CodePlex Archive
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(*\ < on\

(1.)

Azo-1

Thus, the dissociation equilibrium is affected by the ionic strength, temperature and dielectric constant of the solvent as well as by the parameter h (involved in AGfj). On the other hand, the term dG^/dn does not depend on the degree of polymerization (except for very small values of n). The degree of polymerization does not affect, for example, the course of the potentiometric titration of a poly acid. For a dibasic poly acid, where, of the total of T units, nx are ionized to the V first stage and n2 to the second stage, then simultaneously

N=N (K 72 C I)

(2.)

2(n 2 +l)

N=N (K 72 C I)

In 10 x kT 3{nx + n2)

1. Buffer copy CPU moves the data 2. Buffer copy with DMA engine CPU programs the DMA engine DMA engine moves data DMA engine notifies CPU when done

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0.6 Azo-1 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6 Azo-1 (wt%) 96 94 E44 (wt%) 8 10

Here, / is the average distance between two neighbouring doubly ionized monomeric units and e is the effective dielectric constant. For a polyampholyte we have pH = pKlitA - log ocA \-aB aB In 10 x kT dnA 1 SG In 10 x kT

(1.5.23)

0.6 Azo-2 0.5 0.4 0.3 0.2 0.1 0 0 5 10 15 Azo-2 (wt%) 90 85 E44 (wt%) 20 25

(3.)

where K'QA and K^B are the acid dissociation constants of the monomeric unit of the ampholyte, aA = nA/NA and aB = nB/NB, where nA and nB are numbers of ionized acid and basic groups and NA and AB are total numbers f of ionizable acid and basic groups, respectively. These equations are, however, invalid in the vicinity of the isoelectric point where large attractive forces act inside the molecules. A result of this is a decrease of the solubility and coagulation of the polyampholyte. References

0.2 Azo-3

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Fasman, G. D. (Ed.), Prediction of Protein Structure and the Principles of Protein Conformation, Plenum Press, New York 1989 Jurnak, F., and A. McPherson (Eds), Biological Macromolecules and Asemblies, Vol. 2, Nucleic Acids and Interactive Proteins, John Wiley & Sons, New York, 1985. Manning, G., Quart Rev. Biophys., 11, 179 (1978). Morawetz, H., Macromolecules in Solution, John Wiley & Sons, New York, 1965. Oosawa, F., Poly electrolytes, M. Dekker, New York, 1971.

10 15 Azo-3 (wt%) 90 85 E44 (wt%)

Since water as solvent plays the role of a medium where electrolytic displacements take place we shall be able to state for sure, together with Wiedemann, Beetz and Quincke, that the electrical resistance of a solution consists of resistances to movement enforced upon the components of the solution by water particles, by the components themselves and perhaps by the undecomposed molecules of the electrolyte. To separate these various hindrances will be no easy task, particularly because, as stressed by Quincke, they are not necessarily constant but can, for example, depend on the condition of the solution. Even from this standpoint the process of conduction will be, in general, still very complicated. The discussion becomes different when restricted to dilute solutions. In this case one must arrive at the conclusion which essentially helps to simplify the phenomena: In a dilute solution the conductivity depends (besides on the number of dissolved molecules) only on the transported components being independent of their mutual associations. Thus, the more the number of water molecules prevails over those of the electrolyte the more pronounced is the influence exerted by the water molecules on the ions and the less their mutual friction. F. Kohlrausch, 1879

Figure 10.3. Changes in helical pitch as a function of the chiral azobenzene compounds (azo-1, azo-2, and azo-3) in E44 before ( ) and after (D) UV irradiation at 401C.

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