Adsorption Equilibria

Ref: faculty.washington.edu/.../Adsorption%20...
Adsorption Equil Principles_483

If the adsorbent and

adsorbate are contacted long
enough, an equilibrium will
be established between the
amount of adsorbate
adsorbed and the amount of
adsorbate in solution. The
equilibrium relationship is
described by adsorption
isotherms.
 Adsorption Equilibria

An adsorption isotherm is a curve relating the

equilibrium concentration of a solute on the surface of an
adsorbent, qe, to the concentration of the solute in the
liquid, Ce, with which it is in contact.

The adsorption isotherm is also an equation relating the

amount of solute adsorbed onto the solid and the
equilibrium concentration of the solute in solution at a
given temperature.
 Adsorption Equilibria

The adsorption capacity of activated carbon may be

determined by the use of an adsorption isotherm
which can take multiple forms.

Isotherms are found by doing lab tests.

 Adsorption Isotherms

Add same initial target chemical concentration, Cinit, in each

Control

Different activated carbon dosage, Csolid, in each

mg g Co - Ce mg/L or Co - Ce .V = mass
qe or
g g Csolid g/L X mass

An adsorption isotherm is a qe vs. Ce relationship at

equilibrium.
Isotherm models

There are several models for predicting the

equilibrium distribution.
However, the following four models are most
commonly observed.
Commonly Reported Adsorption Isotherms
K Lc
Linear: q klin c Langmuir: q qmax 1 K Lc

Freundlich: q k f c n
 Adsorption Equilibria

i. Linear
ii. Langmuir
iii. Freundlich
iv. Brunauer, Emmet, and Teller (BET)

The most commonly used isotherms for the application

of activated carbon in water and wastewater treatment
are the Freundlich and Langmuir isotherms.
Freundlich isotherm is an empirical equation.
Langmuir isotherm has a rational basis.
Linear Isotherm

qe = K. Ce
 QM
Langmuir Isotherm
It assumes

1. Monolayer coverage,
2. Equilibrium model,
3. All adsorption sites are equally probable,
4. A second order reaction.
 [S.A]
At equilibrium Kad = Eqn 1
[Sv ][A]
Consider total number of sites, ST, to be fixed :
(possible if monolayer coverage is assumed)

ST = [Sv] + [S.A] (moles/m2) Eqn 2

Combining Eqn.s 1 & 2

[S.A]
ST = +[S.A]
K ad [A]
Solve for [S.A] and use CA = [A]

ST K ad .CA .ST
[S.A] = =
1 1+K .C
1+ ad A
K ad .CA

Need expression for qA, which is

mg adsorbate
g adsorbent
q A =[S.A].Aad .MWA

QM .K ad .CA
qA =
1+K ad .CA
or
b.Ce .Q0
qA =
1+ b.Ce
 where

QM or Qo = maximum adsorption capacity for

forming single layer.

Ce has units of mg/L.

Kad or b has units of L/mg.

 Freundlich Isotherm

It is emprical and very widely

used.
1
q e K FCe n

KF is an indicator of adsorption capacity.

Higher the maximum capacity, higher the KF.
1/n is a measure of intensity of adsorption.
Higher the 1/n value, more favorable is the adsorption.
1
Generally, n < 1 1
n
n and KF are system specific constants.
BET (Brunauer, Emmett and Teller) Isotherm

Qo or QM

This is a more general,

multi-layer model. It
assumes that a
Langmuir isotherm
applies to each layer
and that no transmigration occurs between layers.
It also assumes that there is equal energy of
adsorption for each layer except for the first layer.
BET (Brunauer, Emmett and Teller) Isotherm

KB Ce Q0
qe
(CS Ce ){1 (KB 1)(Ce / CS )}
CS =saturation (solubility limit) concentration of the
solute. (mg/liter)

KB = a parameter related to the binding intensity for all

layers.

Note: when Ce << CS and KB >> 1 and Kad = KB/Cs

BET isotherm approaches Langmuir isotherm.
 Most favorable one because
even at low concentrations
you can load your surface
qe with high amounts of material.

Ce

The concept of the adsorption isotherm is

very important, because how much you load
the surface at equilibrium depends on how
much is left in water.
Shape of Freundlich Isotherm
1
q e K FCe n
Determination of appropriate model

To determine which model to use to describe the

adsorption for a particular adsorbent/adsorbate
isotherms experiments are usually run. Data from
these isotherm experiments are then analyzed
using the following methods that are based on
linearization of the models.
For the Langmuir model linearization gives:

Ce 1 Ce
0
qe K Q 0
Q

A plot of Ce/qe versus Ce should give a straight line

with intercept :
1
K Q0

and slope: 1
0
Q
If you obtain a straight line, determine constants
from slope and intercept.
 or:

1 1 1 1
0
qe Q K Q Ce
0

Here a plot of 1/qe versus 1/Ce should give a

straight line with intercept : 1/Qo

1
and slope :
K Q 0
If you obtain a straight line, determine constants
from slope and intercept.
For the Freundlich isotherm use the log-log version :

1
log q e log K F log C
n
A log-log plot should yield an intercept of log KF
and a slope of 1/n.
For the BET isotherm we can arrange the isotherm
equation to get:

Ce KB 1 Ce 1

(CS Ce ) qe KB Q CS KB Q0
0

1
Intercept =
KB Q0

KB 1
Slope = 0
K B Q Cs