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Martin’s rule revisited.: Its molecular sense and limitations

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Title: Martin’s rule revisited.: Its molecular sense and limitations
Authors: Skvortsov, Alexander1, Trathnigg, Bernd2 bernd.trathnigg@uni-graz.at
Source: Journal of Chromatography A. Oct2003, Vol. 1015 Issue 1/2, p31. 12p.
Subjects: Chromatographic analysis, Analytical chemistry, Oligomers, Adsorption (Chemistry), Ethylene
Abstract: The linear relation ln k′=Bn+ln A between the retention factor k′ in liquid adsorption chromatography (LAC) and the number of repeat units n within a homologous series of oligomers is called Martin’s rule. This empirical relation was supported by the retention behavior of the homologous series of different classes of oligomers but had no theoretical justification. In this paper, it is demonstrated that Martin’s rule is a consequence of the general theory of liquid chromatography and the molecular sense of coefficients B and A is clarified: B is the Gibbs energy of the repeat unit of the long polymer chain adsorbed at the wall surface, and A is a combination different parameters which characterize the column and the adsorption correlation length H.The theory predicts the deviations from the linear dependence under conditions of weak adsorption between repeat units and stationary phase when H is close to radius of gyration Rg. Experimental data for retention volumes and selectivity of poly(ethylene glycol)s are given for normal and reversed-phase LAC on different columns in acetone–water and methanol–water as mobile phases. These data show excellent agreement between the theory and experiments. It is shown that Martin’s rule holds under special conditions, which are theoretically defined by the relation H>Rg/1.5. [Copyright &y& Elsevier]
Copyright of Journal of Chromatography A is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: <searchLink fieldCode="DE" term="%22Chromatographic+analysis%22">Chromatographic analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Analytical+chemistry%22">Analytical chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Oligomers%22">Oligomers</searchLink><br /><searchLink fieldCode="DE" term="%22Adsorption+%28Chemistry%29%22">Adsorption (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Ethylene%22">Ethylene</searchLink>
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  Data: The linear relation <F>ln k′=Bn+ln</F> A between the retention factor k′ in liquid adsorption chromatography (LAC) and the number of repeat units n within a homologous series of oligomers is called Martin’s rule. This empirical relation was supported by the retention behavior of the homologous series of different classes of oligomers but had no theoretical justification. In this paper, it is demonstrated that Martin’s rule is a consequence of the general theory of liquid chromatography and the molecular sense of coefficients B and A is clarified: B is the Gibbs energy of the repeat unit of the long polymer chain adsorbed at the wall surface, and A is a combination different parameters which characterize the column and the adsorption correlation length H.The theory predicts the deviations from the linear dependence under conditions of weak adsorption between repeat units and stationary phase when H is close to radius of gyration Rg. Experimental data for retention volumes and selectivity of poly(ethylene glycol)s are given for normal and reversed-phase LAC on different columns in acetone–water and methanol–water as mobile phases. These data show excellent agreement between the theory and experiments. It is shown that Martin’s rule holds under special conditions, which are theoretically defined by the relation <F>H>Rg/1.5</F>. [Copyright &y& Elsevier]
– Name: AbstractSuppliedCopyright
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  Group: Ab
  Data: <i>Copyright of Journal of Chromatography A is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1016/S0021-9673(03)01207-X
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      – Code: eng
        Text: English
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        PageCount: 12
        StartPage: 31
    Subjects:
      – SubjectFull: Chromatographic analysis
        Type: general
      – SubjectFull: Analytical chemistry
        Type: general
      – SubjectFull: Oligomers
        Type: general
      – SubjectFull: Adsorption (Chemistry)
        Type: general
      – SubjectFull: Ethylene
        Type: general
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      – TitleFull: Martin’s rule revisited.: Its molecular sense and limitations
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            NameFull: Trathnigg, Bernd
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              Text: Oct2003
              Type: published
              Y: 2003
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            – TitleFull: Journal of Chromatography A
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