Surface complexation modeling and FTIR study of carbonate adsorption to goethite

被引:178
作者
Villalobos, M [1 ]
Leckie, JO [1 ]
机构
[1] Stanford Univ, Dept Civil & Environm Engn, Stanford, CA 94305 USA
关键词
carbonate adsorption; goethite; surface complexation modeling; inner-sphere complex; ATR-FTIR spectroscopy; surface charge; interfacial charge; charge distribution;
D O I
10.1006/jcis.2000.7341
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Experimental data for carbonate adsorption onto synthetic goethite, spanning 3 orders of magnitude in carbonate concentrations, were simulated using the triple-layer surface complexation model (TLM). A single set of TLM parameters successfully described the adsorption behavior versus pH over the concentration range obtained from closed and open CO2 conditions. An optimization analysis was performed for all possible interfacial charge configurations using FITEQL3.2. The results yielded an optimum charge allocation of 0 and -1 in the 0- and beta -planes, respectively, which suggests a monodentate complex most probably in an inner-sphere configuration (SOCOO-(beta)). Fourier transform infrared (FTIR) spectroscopic measurements on open systems at atmospheric P-CO2 confirmed this result by showing a clear peak split (155 cm(-1)) of the nu (3) C-O asymmetric stretching frequency of surface-bound carbonate, consistent with that reported for monodentate Co(III)-carbonato inner-sphere solution complexes. An additional Naf-ternary complex (SOCOONa) was invoked in the TLM construct to improve simulations of the enhanced carbonate adsorption occurring at high ionic strength and high pH. The model was successful in predicting carbonate adsorption behavior under diffferent conditions than it was calibrated for. Projections for equilibration at higher P-CO2's (1-10%) than those used in this work show the potential for carbonate sorption densities of up to 2.5-3 mu mol/m(2). (C) 2001 Academic Press.
引用
收藏
页码:15 / 32
页数:18
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