Direction and Pressure Response of Osmotic Pressure in Binary Polymer Solutions

Junhan Cho

Macromolecular Research, Vol.25, No.1, 79-84, January, 2017

DOI10.1007/s13233-017-5003-2 Export Citation

Direction and Pressure Response of Osmotic Pressure in Binary Polymer Solutions

Junhan Cho^†

Polymer Science and Engineering Department, and Center for Photofunctional Energy Materials, Dankook University, 152 Jukjeon-ro, Suji-gu, Yongin, Gyeonggi 16890, Korea

E-mail:

Using a molecular equation-of-state (EOS) theory, I discuss the direction and pressure response of osmotic pressure Π for a composite system with a pure solvent and its non-ideal solution of a polymeric component separated by a semi-permeable membrane. A perturbed hard sphere chain model is chosen here for the EOS to estimate Π in a general way while pressure is applied. It is shown that Π is a phase behavior in connection with the phase stability of the solution. In case of an incompatible pair upon forcing a single phase, there exists a region inside the binodal line for negative Π possessing a spinodal point as the threshold of Π=0. It is the potential energy term that contributes to the negative Π and drives solvent molecules away from polymers. Those actions are reversed when phase separation occurs on the solution side. In addition, it is revealed that the solution responds to pressure with either increase or decrease in Π upon pressurization, which depends on the pressure coefficients of spinodals and solvent compressibility.

Keywords:osmosis;negative osmotic pressure;equation of state;pressure response

[References]

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[1] Atkins P, de Paula J, Atkins' Physical Chemistry, Oxford University Press, New York, 2014.

[2] Borg FG, ArXiv:physics, 0305011 (2003).

[3] Ben-Sasson SA, Grover NB, Adv. Physiol. Educ., 27, 15 (2003)

[4] Bolhuis PG, Louis AA, Hansen JP, Meijer EJ, J. Chem. Phys., 114(9), 4296 (2001)

[5] Mezzenga R, Folmer BM, Hughes E, Langmuir, 20(9), 3574 (2004)

[6] Kim J, Chung JS, Kang H, Yu YA, Choi WJ, Kim HJ, Lee JC, Macromol. Res., 22(9), 963 (2014)

[7] Zhong Y, Feng X, Chen W, Wang X, Huang KW, Gnanou Y, Lai Z, Environ. Sci. Technol., 50, 1039 (2016)

[8] Bui NN, Lind ML, Hoek EMV, McCutcheon JR, J. Membr. Sci., 10, 385 (2011)

[9] Richter A, Paschew G, Klatt S, Lienig J, Arndt KF, Adler HJ, Sensors, 8, 561 (2008)

[10] Sperelakis N, Cell Physiology Source Book: Essentials of Membrane Biophysics, Academic Press, Amsterdam, 2011.

[11] Powles JG, Holtz B, Evans WAB, Mol. Phys., 90, 665 (1997)

[12] Cho J, Sanchez IC, Macromolecules, 31(19), 6650 (1998)

[13] Cho JH, Macromolecules, 33(6), 2228 (2000)

[14] Huang K, Statistical Mechanics, 2nd ed., Wiley, New York, 1987.

[15] Chiew YC, Mol. Phys., 70, 129 (1990)

[16] If a Bragg-Williams-type uniform background energy that u(η) ∝ - η is used instead, then the equation of state becomes a generalized van der Waals fluid.

[17] Orwoll RA, Arnold PA, in Physical Properties of Polymers Handbook, Mark JE, Ed., AIP Press, New York, 1996, p 177.

[18] NIST Chemistry Webbook (http://webbook.nist.gov).

[19] Vink H, Eur. Polym. J., 10, 149 (1974)

[20] Noda I, Kato N, Kitano T, Nagasawa M, Macromolecules, 14, 668 (1981)

[21] Callaghan TA, Paul DR, Macromolecules, 26, 2439 (1993)

[22] Roe RJ, Zin WC, Macromolecules, 13, 1221 (1980)