Adsorption Isotherms

presented by

Kazi Monzure Khoda Ph. D. Student SCBE, NTU

1 April 2009

Objective
To present different types of adsorption isotherms using the common chromatographic terms To present different methods which are used to determine the adsorption isotherms

Types of adsorption isotherms

Freundlich adsorption isotherms Langmuir adsorption isotherms BET adsorption isotherms

Langmuir isotherm (red) and BET isotherm (green) 3

Freundlich adsorption isotherms

Published by Freundlich and Kster (1894) Purely empirical formula

where x is the quantity adsorbed m is the mass of the adsorbent C is the concentration of adsorbate k and n are empirical constants for each adsorbent-adsorbate pair at a given temperature

Langmuir adsorption isotherms

Published by Irving Langmuir in 1916

where is the concentration of i in solid phase (adsorbent) is the concentration of i in mobile phase is the partial pressure of component i is the equilibrium constant of component i

Langmuir adsorption isotherms

Langmuir adsorption isotherm

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Langmuir adsorption isotherms

The general Langmuir isotherm for a binary system

If HA>HB

Component A is more retained than B

Now on the basis of PA and PB characteristics Langmuir isotherm can be divided as:
PA PB Name Characteristics

+1
-1 +1

+1
-1 -1

Langmuir
Anti-Langmuir Mixed (M1)

Both components follow the Langmuir isotherm

Both components follow the antiLangmuir isotherm More retained components (A) follow the Langmuir isotherm Less retained components (B) follow the Langmuir isotherm

-1

+1

Mixed (M2)

BET adsorption isotherm

Often molecules do form multilayers Langmuir isotherm is not valid In 1938 Stephan Brunauer, Paul Emmett, and Edward Teller

BET

BET adsorption isotherm

The key assumptions

Solute adsorbs on a flat, uniform surface of the solid Uniform heat of adsorption due to van der Waals forces between the solute and the solid. There is no lateral interaction between the adsorbed molecules The adsorption of the second and subsequent layers occurs with a heat of adsorption equal to the heat of liquefaction of the solute
successive heats of adsorption for all layers except the first

heat of condensation of the adsorbate

BET adsorption isotherm

The derivation of the BET isotherm requires a statistical derivation based on equilibrium considerations

Where na is the adsorbed amount nm is the amount of solute required to form a monolayer of the adsorbate x is the relative concentration, C/Co c is a dimensionless constant greater than one and dependent on temperature

Enthalpy of adsorption for subsequent layers Enthalpy of adsorption for mono layer

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BET adsorption isotherm

Concentration of solute in mobile phase

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BET adsorption isotherm

The two-component BET isotherm expression is given by (Valsaraj et al., 1992):

Where nA is the adsorbed amount nm,A is the amount of solute A required to form a monolayer of the adsorbate x is the relative concentration, C/Co cA= BET isotherm constant for solute A cB= BET isotherm constant for solute B

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Determination of adsorption isotherms

To design and to optimize separations the knowledge of the adsorption isotherms is mandatory Still it appears to be the most difficult task to decide which method is appropriate to determine the adsorption isotherms for a specific separation problem.
References: G. Guiochon, S. Golshan-Shirazi, A. Katti, Fundamentals of Preparative and Nonlinear Chromatography, Academic Press, New York, 1994 A.Seidel-Morgenstern, Experimental determination of single solute and competitive adsorption isotherms. J.Chromatogr. A, 1037 (2004)255-272

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Determination of adsorption isotherms

Static methods
Methods to measure adsorption isotherms
Batch method

Dynamic method
Frontal analysis

Adsorptiondesorption method

Perturbation method

Static method

Dynamic method
Elution by characteristic point Peak fitting method/ inverse method

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Features of different methods capable to measure adsorption isotherms

Method Characterization Special favorable feature Special unfavorable feature Applicable for one solute Applicable for two solutes Applicabl e for more than two solutes Yes Yes

Batch method Adsorption desorption method Frontal analysis method Perturbation method

Static Static Dynamic, large samples Dynamic, small samples Dynamic, intermediate sample Accurate

Tedious, not accurate Tedious

Yes Yes

Yes Yes

Easy automation No detector calibration required

Low sample amount, small number of experiments Isotherm model required High column efficiency required Models for the isotherms and to simulate the chromatogram required

Yes

Yes

Yes

Yes

Yes

Difficult

Elution by characteristic point

Yes

No

No

inverse method

Dynamic, low samples

small number of experiments

Yes

Yes

Difficult

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Conclusion
Further works have to be done to know the details procedure to find out the isotherms experimentally

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THANK YOU

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