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  • 1955-1959  (9)
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  • 1
    Electronic Resource
    Electronic Resource
    Activity of counter ion in polyelectrolyte solutions (1955)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 365-374 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The activity of silver ion was measured potentiometrically with various sample solutions of silver or silver-sodium salt, prepared from three different kinds of carboxymethylcellulose, for the purpose of elucidating these several points: dependence of the activity coefficient of counter ion upon the concentration of polyelectrolyte in salt-free solutions; influence of the silver content of the sample upon activity coefficient; salt effect on activity coefficient; and dependence of activity coefficient upon the degree of neutralization. These experimental results indicate that the characteristics of polyelectrolyte solutions are in many respects quite different from those of simple electrolyte solutions. The applicability of the theory proposed by Ōsawa, Imai, and Kagawa is discussed in some detail, although the discussion is restricted to the salt-free system only.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1955.120178504
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  • 2
    Electronic Resource
    Electronic Resource
    Viscometric behavior of polyacrylate ion in concentrated salt solutions (1955)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 18 (1955), S. 535-542 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosities of polyacrylate ion in the presence of potassium bromide, sodium bromide, lithium bromide, sodium iodide, sodium hydroxide, and hydrochloride acid in aqueous solution were measured over the approximate ranges 0.0-0.6% polymer and salt up to saturation with respect to polyacrylate or to salt. The general initial effect of added electrolyte is to reduce the ratio ηsp/c and to convert the curve characteristic of polyelectrolytes into a straight line, which can be extrapolated to zero polymer concentration to given [η], the intrinsic viscosity of the polymer in the presence of excess salt. Sodium hydroxide and sodium bromide produce minima in plots of [η] against salt concentration. Sodium iodide precipitates polyacrylate at 1.5 N iodide as a translucent gel, which redissolves at 3.0 N and finally reprecipitates at 6 N. In the latter range of concentration, [η] exhibits a maximum. Both by-ions and counter-ions have specific effects on the viscosity of the polyion.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1955.120189009
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  • 3
    Electronic Resource
    Electronic Resource
    Colligative properties of polyelectrolyte solutions. VI. Donnan membrane equilibrium (1959)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 38 (1959), S. 213-228 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Donnan membrane equilibrium of a linear polyelectrolyte solution was studied, using sodium polyvinyl alcohol sulfate as the sample and sodium chloride as the diffusible salt. Simultaneous measurements of membrane potential, sodium and chloride ion activities, sodium chloride distribution, osmotic pressure, and viscosity were carried out. The measurements of membrane potential and ionic activities gave consistent results which could be accounted for by the Donnan theory. The second virial coefficient, which was found to be much lower than the ideal Donnan term, was examined according to Scatchard's theory. It was found that while the theory gave a good qualitative explanation to the experimental results, it could not be used for quantitative discussion. For quantitative examination of the experimental second virial coefficient, the value of second virial coefficient was calculated from the assumption that osmotic pressure is proportional to the difference of the sum of solute activities on both sides of membrane, and was found to be nearly equal to the observed value.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1959.1203813319
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  • 4
    Electronic Resource
    Electronic Resource
    Theory of the effect of counterion size upon titration behavior of polycarboxylic acids (1957)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 23 (1957), S. 477-484 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of the ionic radius of counterions has been introduced into the dissociation theory of polyelectrolytes, using the familiar rod-like model. Increments in the average dissociation constant pKa and slope n for polyacrylic acid with increasing size of the gegenion have been calculated and compared with data using potassium and some tetraalkylammonium hydroxides. Good agreement is encountered. The effects of changes in concentration of the polyacid and of the presence of neutral salt are also considered.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1957.1202310340
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  • 5
    Electronic Resource
    Electronic Resource
    Colligative properties of polyelectrolyte solutions. IV. Activity coefficient of sodium ion (1958)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 31 (1958), S. 256-256 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1958.1203112257
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  • 6
    Electronic Resource
    Electronic Resource
    Colligative properties of polyelectrolyte solutions. V. Activity coefficients of counter- and by-ions (1959)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 37 (1959), S. 375-383 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Simultaneous measurements of the activity coefficients of counter- and by-ions in polyelectrolyte solutions were carried out. Sodium polyvinyl alcohol sulfate was used as the sample of polyelectrolyte and sodium chloride as the extraneous salt. The activity coefficient of sodium counter-ion was determined by using a sodium amalgam electrode and that of chloride ion was determined by a sliver-silver chloride elctrode. It was found that the activity coefficient of both counter- and by-ions has little relationship with the volume of polymer coil, and that the additivity of counter-ion activity found for hydrogen ion by Mock and Marshall holds also for sodium ion. It was also found that there is good agreement between the experimental results and the theory of Katchalsky and Lifson if we use their same theory for calculating the volume of polymer coil, although the volume is too large to be considered reasonable.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1959.1203713208
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  • 7
    Electronic Resource
    Electronic Resource
    Statistical thermodynamics of polyelectrolyte solutions. I. Activity coefficient of counter ion in salt-free system (1955)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 16 (1955), S. 299-310 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The authors investigated theoretically the activity coefficient of counter ion in the salt-free polyelectrolyte solutions, by stressing the interionic interaction between the macro ion and counter ion. Assuming the Boltzmann distribution for the polyelectrolyte system and proposing a new linear approximation, the Poisson-Boltzmann equation was solved for a model of spherical rigid macro ion, and then the free energy of the system was calculated by means of the charging-up procedure. Applying this theory to the experimental data of activity coefficient of silver ion in the silver carboxymethyl cellulose solutions, the size of macro ion was computed, and the results are discussed from a purely theoretical standpoint. Thus, the authors have succeeded in giving a valid insight into the correlation between polyelectrolyte and simple electrolyte solutions as well as into some peculiar features of polyelectrolyte solutions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1955.120168219
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  • 8
    Electronic Resource
    Electronic Resource
    Colligative properties of polyelectrolyte solutions. IV. Activity coefficient of sodium ion (1957)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 25 (1957), S. 61-76 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By the concurrent use of the ion exchange membrane electrode in addition to the sodium amalgam electrode, the ionic activity of sodium ion in salt-free polyelectrolyte solutions was determined over a considerably wide range of sample concentration. As polyelectrolyte samples, several kinds of sodium polyvinyl alcohol sulfates differing in their degrees of esterification and degrees of polymerization (sodium polystyrene sulfonate, sodium cellulose sulfate, and carboxymethylcellulose) were used. The peculiar dependency of the activity coefficient of sodium ion upon the sample concentration first noted by Kern was confirmed with all samples in this study; that is, γNa+ decreases with dilution of the sample solution. Further, it was confirmed that the degree of esterification, viz., the charge density on a linear polymer, is a most important factor while the activity coefficient is entirely independent of the degree of polymerization. The influence of structure of the polymer skeleton upon the activity coefficient was found to be comparatively small. Some of the above results were discussed on the basis of the authors' theory published in a previous paper.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1957.1202510806
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  • 9
    Electronic Resource
    Electronic Resource
    Electrophoresis of polyelectrolyte in salt solutions (1958)
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 31 (1958), S. 439-451 
    Details
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some measurements of the electrophoretic velocity were carried out on sodium polyvinyl alcohol sulfates. The intrinsic mobility of the polyion in sodium chloride solutions was obtained by extrapolating the values at various polymer concentrations. The extrapolating value at the zero polymer concentration was the same for both descending and ascending boundaries. The mobility of polyion vs. sodium chloride concentration curve thus obtained showed the following features. (a) At zero NaCl concentration the mobility of polyion quite agrees with the mobility of the monomer acid. (b) In the limit of sufficiently concentrated NaCl solution, the mobility also approaches the mobility of the monomer acid. (c) In the intermediate state between these two limits, measured mobilities of polyion are always larger than the mobility of the monomer acid. Accordingly, there is a maximum of the mobility at a certain NaCl concentration. These experimental results were analyzed in terms of the theory of Hermans and Fujita on the electrophoresis of coiled polyelectrolyte, and it was found that their theory gives a satisfactory (at least qualitatively) explanation of our experimental data.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1958.1203112322
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