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Theory of Gel Chromatography

Mechanism of Separation

  • The separation mechanism is based on the size (hydrodynamic volume) of molecules relative to the pore sizes of the gel beads in the stationary phase.

Exclusion:

  • Molecules: Larger than the largest pores.

  • Behavior: Excluded from entering the beads.

  • Elution: Pass straight through, eluting first.

Partial Penetration:

  • Molecules: Smaller than the largest pores but larger than the smallest.

  • Behavior: Enter some pores partially.

  • Elution: Delayed compared to excluded molecules.

Total Penetration:

  • Molecules: Small enough to enter all pores.

  • Behavior: Spend the most time within the column.

  • Elution: Pass through the column last.

Elution Volume

  • Definition: The volume at which a molecule elutes from the column.

  • Relation to Size:

    • Larger Molecules: Smaller elution volume (elute first).

    • Smaller Molecules: Larger elution volume (elute last).

Partition Coefficient (Kav)

  • Definition: Describes the behavior of a molecule in the column.

  • Calculation:

Partition Coefficient (Kav)
  • Ve: Elution volume of the molecule.

  • V0: Column void volume (volume outside the pores).

  • Vt: Total column volume.

Relation to Molecular Size:

  • A calibration curve is created by plotting Kav​ values of standards with known molecular weights.

  • The molecular weight of unknown molecules is determined using their elution volumes and corresponding Kav​ values.


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