It is appaxent that whatever the effect of adding ketone to the fluoroalcohols may be, it is not ume with con~entration.~~ present in the case of the hydrocarbon alkanols since they exhibit no change in partial molar vol-(17) The Reviewer pointed out that part of the partial molar volume change of fluoroalcohols with ketones may be due t o the interaction of the perfluoroalkyl (chain with the alkyl groups of the ketone rather than to hydrogen bonding. The mixin,. of hydrocarbons with fluorocarbons is accompanied by large positive volume changes (up to 5% increase).A study of the binding of silver by imidazole and polyvinylimidazole in 1 M potassium nitrate showed two-fold coordina-These values are almost The polymer bound silver somewhat more strongly (log klkz = 8.00), with Also, with the polymer, binding was found to occur a t much lower pH tion. the same a8 corresponding ones for ammonia. the second step being much stronger than t,he first.Forniation iconstants for the tR*o steps with imidazole were: log kl = 3.11; log k2 = 3.73.levels, as compared Gith the monomer.
The reduced specific viscosity of polymethacrylic acid increased with counterion size at the same degree of neutralization for the cations: sodium < tetramethylammonium < tetraethylammonium < tetrapropylammonium < tetrabutylammonium. The increase on going from sodium to tetrapropylammonium at 50–70% neutralization was 20–25% for 0.003–0.01 M polymer, about 4% in 0.001 M solutions. These data indicate that a significant fraction of even large counterions are close to the chain. Conductometric titrations showed that the equivalent conductance of the polyanion was about 40 for most of the salts studied and at low values of α. The binding of counterions based upon the assumption that this value was constant over α led to values which were in reasonable agreement with those determined by Wall using transport experiments.
15) This is in agreement with some recent unpubliahed results obtained in our laboratory.The viscosity of poly-N-vinylmethylimidazolium salts over the concentration range 0.0001-0.006M (base moles) followed the expression c/vSp = A + Bdi; specific viscosities decreased in the series: iodide > trichloroacetate > chloride.,The conductance of a series of salts in the same concentration range could be expressed by the equation A0 -A .= dE/(c -k G d c ) . The calculated value of the limiting polycation conductance (per base mole) was 25 for the chlonde, bromde, nitrate, iodide and iodate polysalts, and 60 for the trichloroacetate and p-toluenesulfonate salts. Making uae of counterion concentrations calculated from 01 = A / A~, it was found that the data fitted the Henderson-Hasselbalch expressipn which contained a term for the ionic strength, p [CCY] = pK -2 log [( 1 -01)/01 J -+d/cLu. Association of the olysalts increased in the sequence: iodate < chloride < bromide nitrate < trichloroacetate < p-toluenesulfonate < iogde.
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