ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2009, Vol. 83, No. 3, pp. 457464. Pleiades Publishing, Ltd.

., 2009. Original Russian Text A.V. Pastukhov, V.A. Davankov, M.P. Tsyurupa, Z.K. Blinnikova, N.E. Kavalerskaya, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 3, pp. 541549.

PHYSICAL CHEMISTRY OF NANOCLUSTERS AND NANOMATERIALS

The Contraction of Granules of Nanoporous Super-Cross-Linked Polystyrene Sorbents as a Result of the Exclusion of Large-Sized Mineral Electrolyte Ions from the Polymer Phase
A. V. Pastukhova, V. A. Davankova, M. P. Tsyurupaa, Z. K. Blinnikovaa, and N. E. Kavalerskayab
a Nesmeyanov

Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, GSP-1, 119991 Russia b Faculty of Chemistry, Moscow State University, Moscow, 119992 Russia e-mail: avpastukhov@mail.ru
Received April 8, 2008

AbstractThe deformation of neutral super-cross-linked polystyrene sorbents and ionites based on styrene divinylbenzene gel-type copolymers brought in contact with concentrated solutions of HCl, H3PO4, NaOH, NH4Cl, (NH4)2SO4, and LiCl electrolytes was studied by dilatometry for separate spherical granules. Considerable contraction of super-cross-linked polystyrene matrices swollen in water was observed in concentrated solutions containing large-sized lithium, sulfate, and phosphate ions. Volume compressive strain correlated with the size of excluded hydrated ions. The contraction effect was caused by the difference in the osmotic pressure of water in thin pores and water in concentrated solutions lling large pores. The exclusion effect ignored earlier should also inuence the degree of ion exchange and volume deformation of standard ion-exchange resins brought in contact with solutions of various electrolytes. DOI: 10.1134/S0036024409030236

INTRODUCTION Studies of the deformation behavior of polymeric sorbents and ionites, which experience substantial thermal, mechanical (caused by pressure drop in columns), or osmotic (when the composition of contacting liquids change) action during their service life, are of importance for prolonged, effective, and safe use of these materials in sorption and chromatographic technologies. In recent years, super-cross-linked polystyrenes have been nding ever increasing use as a new class of high-efciency neutral and ion-exchange sorbents [1]. Thanks to their unique rigid nanoporous structure, they exhibit exceptionally high sorption capacity combined with high mass exchange rates and ease of regeneration. Super-cross-linked polystyrenes are drastically different from all the known network polymers of the gel and macroporous types also because of their unusual deformation properties under mechanical, thermal, or solvent actions [24]. Neutral super-cross-linked polystyrenes not only are highly effective sorbents of organic compounds but also offer much promise for the separation of inorganic salts, acids, and bases because of the exclusion of larger ions from nanosized sorbent pores. Indeed, hydrated mineral ions can be as large as 0.80.9 nm in diameter, whereas super-cross-linked polystyrene matrix pores and channels have statistical size distributions with maxima at 23 nm [5]. The pronounced sieve effect,

that is, the inaccessibility of the thinnest matrix pores to some mineral ions, was used to create and successfully develop a new preparative chromatographic method, the frontal exclusion chromatography of electrolytes [6, 7]. As distinct from ion exchange, this method is especially effective in processing concentrated mineral solutions. For this reason, the problem of the stability of sorbent volume in columns is of special importance. In this work, we used dilatometry to study changes in the volume of neutral super-cross-linked polymers brought in contact with concentrated solutions of inorganic electrolytes. It was found for the rst time that the exclusion of large-sized ions from thin sorbent pores caused granule contraction because of the difference in osmotic pressure between these pores and the external concentrated solution of electrolytes. For comparison, standard ion-exchange gel sorbents were studied under the same conditions. Volume changes of these sorbents are much more substantial, but are primarily caused by quite different reasons. EXPERIMENTAL The objects of study were super-cross-linked polystyrenes synthesized as described in [8] and based on granulated styrene copolymers of the gel type, which largely contained nanopores, and a commercial sorbent, super-cross-linked polystyrene NN381 (Purolite Int, Great Britain). For comparison, we studied gel ionites based on styrenedivinylbenzene copolymers,

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