By Herbert August Laitinen, Walter E. Harris
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Extra resources for Chemical Analysis: An Advanced Text and Reference
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When molecules of different sizes are mixed, the resulting system has increased entropy; this effect would be expected to lead to lowering of the activity coefficient. The contribution of the size has been expressed by34 where r is the ratio of partial molar volumes of solvent and solute. This term has been estimated34for several solutes in hydrocarbons of high molecular weight, and negative values in the region of a few tenths to about 1 unit in In y , have been obtained. Equation (2-40) indicates that the size effect is small for solute and solvent molecules of the same size.
To illustrate, if the dibasic acid H,A is added to water, we have the equilibria H2A =$H' and HA- H' + HA+ A= Kl = LH'IIHA-I (3-32) [Hz A1 K2 = [H'l[A=l wA-1 (3-33) These, together with the stoichiometric equation and the electroneutrality condition [H'] = [HA-] + 2[Az] (3-35) give four equations and four unknowns. Rigorous solution of the equations can be awkward; fortunately, it can be avoided by simple approximations. As a first approximation, ignore the second ionization step. Thus and from Equation (3-21) [H']' = ~ K ~ ( C ,-, ~[H']') (3-37) as for a monobasic acid.