TY - JOUR
T1 - Phase behavior of polyelectrolyte solutions with salt
AU - Lee, Chi Lun
AU - Muthukumar, Murugappan
N1 - Funding Information:
It is a pleasure to thank Mr. Bernhard Fischer for his contributions during the initial stage of this project. Acknowledgment is made to the National Science Foundation Grant No. DMR-0605833, and the Materials Research Science and Engineering Center at the University of the Massachusetts, Amherst.
PY - 2009
Y1 - 2009
N2 - We have computed the phase diagrams of solutions of flexible polyelectrolyte chains with added simple electrolytes. The calculations are based on our recent theory [M. Muthukumar, Macromolecules 35, 9142 (2002)], which accounts for conformational fluctuations of chains, charge density correlations arising from dissolved ions, hydrophobic interaction between polymer backbone and solvent, and translational entropy of all species in the system. The theory is at the mean field level and recovers the results of the restricted primitive model with the Debye-Hückel description for solutions of simple electrolytes without any polymer chains and those of the Flory-Huggins and scaling theories for uncharged polymers in the absence of charges or electrolytes. In constructing the phase diagrams, the chemical potential of each of the species is maintained to be the same in the coexisting phases and at the same time each phase being electrically neutral (Donnan equilibrium). Comparisons are made with a more constrained situation where the chemical potentials of the independent components are maintained to be the same in the coexisting phases. Our calculations predict several rich phenomena. Even for the salt-free solutions, two critical phenomena (corresponding to the Flory-Huggins-type and the restricted-primitive-model-type critical points) are predicted. The coupling between these two leads to two critical end points and triple points. In the presence of salt, the valency of electrolyte ions is found to influence drastically the phase diagrams. Specifically, the predicted liquid-liquid phase transitions in certain temperature ranges is reminiscent of the re-entrant-precipitation phenomenon observed experimentally for polyelectrolytes condensed with trivalent salts.
AB - We have computed the phase diagrams of solutions of flexible polyelectrolyte chains with added simple electrolytes. The calculations are based on our recent theory [M. Muthukumar, Macromolecules 35, 9142 (2002)], which accounts for conformational fluctuations of chains, charge density correlations arising from dissolved ions, hydrophobic interaction between polymer backbone and solvent, and translational entropy of all species in the system. The theory is at the mean field level and recovers the results of the restricted primitive model with the Debye-Hückel description for solutions of simple electrolytes without any polymer chains and those of the Flory-Huggins and scaling theories for uncharged polymers in the absence of charges or electrolytes. In constructing the phase diagrams, the chemical potential of each of the species is maintained to be the same in the coexisting phases and at the same time each phase being electrically neutral (Donnan equilibrium). Comparisons are made with a more constrained situation where the chemical potentials of the independent components are maintained to be the same in the coexisting phases. Our calculations predict several rich phenomena. Even for the salt-free solutions, two critical phenomena (corresponding to the Flory-Huggins-type and the restricted-primitive-model-type critical points) are predicted. The coupling between these two leads to two critical end points and triple points. In the presence of salt, the valency of electrolyte ions is found to influence drastically the phase diagrams. Specifically, the predicted liquid-liquid phase transitions in certain temperature ranges is reminiscent of the re-entrant-precipitation phenomenon observed experimentally for polyelectrolytes condensed with trivalent salts.
UR - http://www.scopus.com/inward/record.url?scp=58449091519&partnerID=8YFLogxK
U2 - 10.1063/1.3054140
DO - 10.1063/1.3054140
M3 - 期刊論文
C2 - 19154053
AN - SCOPUS:58449091519
VL - 130
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 2
M1 - 024904
ER -