Intra-particle sorption rate and liquid chromatographic bandbroadening in porous polymer packings .1. Methodology and validation of the model

被引:22
作者
Gowanlock, D [1 ]
Bailey, R [1 ]
Cantwell, FF [1 ]
机构
[1] UNIV ALBERTA,DEPT CHEM,EDMONTON,AB T6G 2G2,CANADA
基金
加拿大自然科学与工程研究理事会;
关键词
band broadening; sorption; stationary phases; LC; polymer packings; porous; thermodynamic parameters; kinetic studies;
D O I
10.1016/0021-9673(95)01018-1
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
An approach is proposed by which an experimentally measured sorption-rate curve for a solute on a chromatographic sorbent may be used to accurately predict the plate height and peak shape contributions of intra-particle sorption rate to the chromatographic peak that will be obtained when the solute elutes from a liquid chromatographic column of the sorbent. The sorption-rate curve is measured on a ''shallow bed'' of sorbent (e.g. approximate to 1 mm) under ''infinite solution volume'' conditions and is fit by an empirical tri-exponential equation. Intra-particle rate processes include the bandbroadening phenomena traditionally identified by the H-s and H-SM plate-height terms. The elution chromatographic column is imagined to be composed of three ''hypothetical columns'' in series, and the hypothetical peak eluting from each is calculated from well-known equations. Numerical convolution of these hypothetical peaks in series yields the overall predicted elution peak contribution from intra-particle rate processes. The accuracy of this model is demonstrated by comparing predicted peaks with eluted peaks measured on a long column of very large diameter (0.36 mm) porous polymer sorbent. On this column, chromatographic bandbroadening is due nearly exclusively to slow intra-particle processes. The proposed approach is not limited, either theoretically or in practice, to large particles or to porous polymers.
引用
收藏
页码:1 / 23
页数:23
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