Schroeders paradox is the different equilibrium degree of swelling for a hydrophilic polymer in saturated aqueous vapor and in liquid

water. In a closed vial filled with water, a gelatin plate was immersed in a liquid to half its length the gelatin used by Schroeder met these conditions and
exhibited a 25-fold increase in swelling upon the transition from saturated vapor to water.

250 200 esw , % 150 100

vapor

C-104 A-850
liquid

liquid

50 0 0 2000 4000

vapor

6000

8000

Time, s

An even stronger Schroeder effect is observed for gel ion-exchangers of a polyacrylate nature: A-850 anionite and C-104 weak cationite. The polymers maximum volume increase attains a value of 200240%, and the jump in swelling from vapor to liquid water is two to three times as great. Paradoxes of Thermodynamics of Aqua-Vapor-Polymer Interface Equilibrium V. A. Davankov and A. V. Pastukhov Russian Journal of Physical Chemistry A, 2011, Vol. 85, No. 5, pp. 721729.

ISSN 0036 0244, Russian Journal of Physical Chemistry A, 2011, Vol. 85, No. 5, pp. 721729. Pleiades Publishing, Ltd., 2011. Original Russian Text V.A. Davankov, A.V. Pastukhov, 2011, published in Zhurnal Fizicheskoi Khimii, 2011, Vol. 85, No. 5, pp. 805814.

Paradoxes of Thermodynamics of AquaVaporPolymer Interface Equilibrium

V. A. Davankov and A. V. Pastukhov
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia e mail: davank@ineos.ac.ru
Received June 23, 2010

AbstractSchroeders paradox is the different equilibrium degree of swelling for a hydrophilic polymer in saturated aqueous vapor and in liquid water; it is experimentally verified by the registration of increasing vol ume of spherical polymer samples upon the processes of vapor and liquid water sorption. Specimens of three main classes of hydrophilic cross linked polymers were tested. These had gel, hypercrosslinked, and macroporous structures that differed by the scale of the Schroeder effect. A similar effect is typical also for hydrophobic polymers upon swelling in liquid organic solvents and their saturated vapor. The paradox is explained by the lower activity of a sorbate in a saturated vapor compared to its activity in a liquid phase. The ability of many samples of cross linked polymers with different degrees of saturation with a sorbate to be at equilibrium with the saturated vapor of a sorbate is explained by the differences in the inner structure of these samples, i.e., by differing in the swelling combinations and the intensity of the interchain interactions in a polymer network. Keywords: interphase equilibria, paradoxes of thermodynamics, hydrophylic polymers, degree of saturation, sorbate. DOI: 10.1134/S0036024411050098

INTRODUCTION It is well known to specialists in the field of sorption technologies that ion exchange resins increase their volume in a wet atmosphere and even more strongly in aqueous media. At each of these two phases of polymer swelling, enormous forces (swelling pressure) arise that can break a column initially filled with a dry ion exchange resin. As early as 1903, Schroeder published the results of a simple experiment: in a closed vial filled with water, a gelatin plate was immersed in a liquid to half its length [1]. After equilibrium was achieved in the system, it was found that the moisture content in the upper part of the sample (which was in contact only with saturated water vapor) was much less than that of the part of the plate immersed in water. Accord ing to this experiment, a gelatin plate brought into a contact with saturated vapor greatly increases its vol ume upon immersion in liquid water. The considerable distinction between the equilib rium swelling of a hydrophilic polymer in vapor and in liquid water (Schroeders paradox) still has no clear phenomenological explanation and strict thermody namic description. The authors of this work aim to rectify this deficiency. First, we act on the premise that repeatedly confirmed Schroeders effect clearly dem onstrates the higher activity of liquid water compared to the activity of water in a saturated vapor, and this claim should be true for any equilibrium liquid and

saturated vapor. Second, taking into account the prin cipal differences in the structure of gel, macroporous, and hypercrosslinked polymer networks, we predict and explain the considerable differences between the values of Schroeders effect that are typical for these different types of polymer materials. Thermodynamic of LiquidVapor Equilibrium The basic thermodynamics postulated for an equi librium single component heterogeneous liquidsat urated vapor system is the equality of the chemical potentials of a substance (e.g., water) in these phases: (1) w = w, which is usually represented by the empirical ratio

w + RT ln a w = w + RT ln a w ,

(2)

where w , w , w , and w are the chemical potentials and standard chemical potentials of vapor and liquid water, respectively. In 1975, IUPAC defined a pure substance ( = 1) in the state of an ideal gas with a pressure of = 1 atm (1.01 105 Pa) at any fixed temperature as the standard state for all gaseous substances. At the same time, these conditions are apparently not strictly fixed, since less precise definitions for a gas are found in the literature, such as The standard value () is the chemical potential at unitary pressure (e.g., 1 atm) [2, p. 229].

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