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Deviations from Beer-Lambert Law

  • Situations where Beer-Lambert Law may not hold include:

Chemical Deviations:

  • Association/Dissociation: At high concentrations, molecules may associate or dissociate, altering the absorbing species.

  • Reactions with Solvent: Chemical interactions between solute and solvent can change the nature of the absorber.

Instrumental Deviations:

  • Stray Light: Light outside the selected bandwidth can cause overestimated absorbance.

  • Polychromatic Radiation: Non-monochromatic light may lead to errors, especially for samples with sharp absorption peaks.

Physical Deviations from Beer-Lambert Law:

  • High Concentrations: Changes in refractive index can affect absorption at very high solute concentrations.

  • Temperature/Solvent Effects: Variations in solvent or temperature can alter peak shape and position.

  • Light Scattering: Particles or droplets scatter light, distorting absorbance readings.


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