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Published on: September 2, 2020
Critical chromatography in ternary solvents
Matthäus Mlynek1, Wolfgang Radke
1Fraunhofer Institute for Structural Durability and System Reliability LBF, Division Plastics, Schlossgartenstraße 6, D-64289 Darmstadt, Germany.
Mixing two critical eluents for polymer analysis does not guarantee constant elution. Elution behavior in size exclusion chromatography (SEC) and liquid adsorption chromatography (LAC) can be unpredictable due to adsorption. Ternary critical conditions can predict elution modes.
Area of Science:
- Polymer Science
- Chromatography
- Analytical Chemistry
Background:
- Size Exclusion Chromatography (SEC) and Liquid Adsorption Chromatography (LAC) are key techniques for polymer analysis.
- Critical conditions in chromatography aim for molar mass-independent elution, simplifying analysis.
- The behavior of polymers like PMMA in mixed eluents is complex and not fully understood.
Purpose of the Study:
- To investigate the elution behavior of PMMA standards in mixtures of two binary critical eluents.
- To understand why combinations of critical eluents deviate from predicted critical conditions.
- To develop a method for predicting elution modes when mixing critical eluents.
Main Methods:
- Experimental investigation of PMMA standards' behavior in binary critical eluent mixtures.
- Analysis of elution modes including SEC, LAC, and near-critical conditions.
- Estimation of ternary critical conditions using gradient experiments to predict elution behavior.
Main Results:
- Combinations of two critical eluents did not achieve molar mass-independent elution (critical conditions).
- Elution occurred unpredictably in SEC, LAC, or near-critical modes when mixing eluents.
- Preferential adsorption of eluent components to the stationary phase or polymer is hypothesized as the cause of deviation.
- Estimated ternary critical conditions showed good agreement with observed elution behavior in mixed eluents.
Conclusions:
- Mixing two critical eluents does not reliably yield critical conditions for PMMA analysis.
- Adsorption effects significantly influence elution behavior in mixed eluent systems.
- Estimating ternary critical conditions provides a reliable method for predicting elution modes in such systems.
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