Outline

ENVE 322
1. Definitions of adsorption process
Transport Processes in
Environmental Engineering 2. Three Isotherms: Linear, Langmuir and Freundlich
3. Their adoption to Mass Balance

Lecture 12 – Adsorption & Desorption

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Learning objectives Some Definitions

If you learned the topic, you should be able to:
• define adsorption, desorption, sorption and absorption
• list the mechanisms important for adsorption
• use isotherm calculations to calculate the mass in a
given system (by adopting it to mass balance equation)
Adsorption is the accumulation of a chemical at the interface
between the two phases (usually, a solid and a fluid; e.g., liquid-
solid and gas-solid interfaces). Adsorption should not be
confused with absorption. Adsorption is a surface phenomenon
in which chemical accumulates at solid surface.
Absorption is a bulk phenomenon in which a chemical becomes
distributed throughout a solid or liquid adsorbent. The term
sorption is commonly used to include both phenomena,
adsorption and absorption. When the sorption onto solids is
emphasized, most commonly it is known as adsorption.

Desorption is the inverse of adsorption being the release of

adsorbed chemicals back into the fluid phase.

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 Adsorption Mechanisms
Solids (sorbents) capable of sorbing chemicals (sorbates)
include minerals, such as clays and metal oxides; natural
organic material; and plastic, for example, polyvinyl
chloride (PVC), commonly used in groundwater monitoring
wells.
The mechanisms by which sorption can occur include
absorbtion into natural organic matter; adsorption to
mineral surfaces via van der Waals, dipole-dipole, and
other weak physical intermolecular forces; adsorption
through eloctrostatic atractions to oppositely charged
surface sites on the solids; and adsorbtion through
covalent bonding to surface groups on the solids.
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Adsorption – Desorption Examples (cont.)
Adsorption can be applied to transfer of contaminants from a fluid
(air or water) to the surface of a solid material for subsequent
treatment or disposal. For example;
In drinking water treatment, adsorption is often used for taste and
odor control, and for removal of toxic organic contaminants from
water.
In air quality engineering, adsorption is applied to limit the
release of trace organic gases from industrial prcesses.
In groundwater pollution control, hydrocarbon contaminants
adsorb to soil particles, slowing their movement through the
aquifer.
In wastewater treatment, metals adsorb to microbial cells in
biological treatment systems, enhancing their removal.
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Adsorption – Desorption Examples
Adsorption and desorption of chemicals
(adsorbates) at liquid-solid and gas-solid
interfaces (adsorbents) are common phenomena
in natural and engineered environmental systems.
Examples include adsorption of chemicals
•on sediments, suspended matter, soil and
aeresols in natural systems and
•onto activated carbon, zeolite, geosynthetic clays
and ion exchange resins in engineered systems.
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Equilibrium Partitioning
The equilibrium partitioning of a chemical between a fluid
phase and the sorbed phase is described by semiempirical
relationships called sorption/adsorption isotherms or simply
isotherms. Isotherms typically describe the equilibrium
relationship between two quantities:
i. the mass of sorbed contaminant per mass of sorbent
(solid);
ii. the equilibrium concentration of contaminant in the fluid
(mass or molar concentration in water, or partial
pressure in air).
Use of the term isoterm indicates that sorption
measurements are made under constant temperature.
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 Isotherms Isotherms (cont.)

Functional forms of semi empirical In these equations, Cw is the equilibrium

isotherms are based on Linear: C ads = K d C w

Adsorbed Concentration, Cads (mg/g)

concentration in fluid (water), mg or mol of
thermodynamic arguments, but they chemical per liter of fluid; Cads is the equilibrium
include data that can be obtained mass of adsorbed mass per mass of sorbent,
only from experiment. Although a max bC w mg or mol of chemical per g of sorbent; Kd is a
Langmuir: C ads =
many isotherm forms have been 1 + bC w solid-liquid distribution coefficient, liter of fluid
developed, three common froms per g of sorbent; amax is the adsorption capcity,
are as follows; mg of chemical per g of sorbent; b is the
Fruendlich: Cads = K F Cw1 / n adsorption affinity parameter, liter of fluid per
Linear: C ads = K d C w mg of chemical; KF is a Freundlich parameter
and n is a nonlinearity factor.
a max bC w The symbol Kd is frequently used to represent a solid-water partition coefficient;
Langmuir: C ads =
1 + bC w which is also called as a distribution coefficient. The use of a constant coefficient
Dissolved Concentration, Cw (mg/L) Kd implies a linear relationship between the amount of dissolved and sorbed
contaminant. In actuality, this relationship is often nonlinear.
Freundlich: Cads = K F Cw1 / n
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Isotherms (cont.) Isotherms (cont.)

In linear isotherm, the adsorbed The Freundlich isotherm provides an

mass of contaminant (Cads) alternative description that applies to

ads
Adsorbed Concentration, Cads (mg/g)

increases in direct proportion to the cases with surface heterogeneties,

dissolved contaminan concentration which result in a distribution of High afinity
(Cw) with no maximum. By contrast, adsorption energies at surface sites. In
in a Langmuir isotherm, the sorbent a Freundlich isotherm, KF is related to
can become completely saturated, adsorption capacity (at the higher KF
leading to a maximum adsorption values the more mass potentially
capacity (amax). In a Langmuir adsorbed; n is related to the afinity of Low afinity
isotherm higher values of amax and contaminant for the surface (the
b mean high adsorption capacity smaller the n value the greater the
and high chemical affinity to affinity of contaminant for the surface).
adsorption, respectively. Note that for n=1, Freundlich isotherm
Dissolved Concentration, Cw (mg/L)
is linear and KFºKd.

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 Isotherms (cont.) Mass balance and solid-liquid partitioning

Usually, the adsorption/desoption processes are very fast, Mass balance and solid-liquid partition:
attaining equilibrium condition within minutes or hours. Consider a well mixed batch reactor of
This implies that in environmental systems where the time volume, V, (V=area x depth = A x h) filled
scale is in the order of days, the assumption of equilibrium with wastewater containing dissolved
can be justified. However, if it is necessary to include the volatile toxic substance of concentration
Cw and suspended solid particles of
rate expression, a first-order type expression can be
concentration Pw. In the reactor,
assumed to give the rate of transfer as suspended solid particles settles due to
gravity with a settling velocity of vs. Notice
= k (C eq - C ads )
dC ads
that the toxic substance is partitioned into
dt dissolved (water) fraction and particulate
where Ceq is the equilibrium concentration on the solid (solid) fraction via sorption; and that
phase; and k is adsorption rate coefficient, T-1. volatilization and settling act selectively on
these components.

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Mass balance and solid-liquid partitioning (cont.) Mass balance and solid-liquid partitioning (cont.)

Mass of dissolved conta min ant Mw Dissolved chemical

Cw = = Þ concentration
Now, let us consider mass balance for dissolved and adsorbed toxic V
Volume of water
chemical, and suspended particles subjected selectively to settling,
sorption and volatilization. Let us define the following concentrations: The amount of total mass within the system, MT, is the sum of adsorbed
mass, Mads, and dissolved mass, Mw:

Mass of suspended solid particles Mp M T = M ads + M w = Cads PwV + CwV = C pV + CwV

Pw = = Þ Suspended solid concentration
V
Volume of water
where Cads is related Cw by adsorption isotherm. Assume that partition
Mass of conta min ant adsorbed onto particles M ads Adsorbed chemical between solid and water is described by a linear adsorption isotherm.
C ads = = Þ concentration in solid
Mp phase
Mass of suspended solid particles
MT
Adsorbed C ads = K d C w Þ M T = K d C w PwV + C wV Þ CT = = (K d Pw + 1)C w
Mass of adsorbed conta min ant M ads M p M ads chemical V
Cp = = = PwCads = Þ concentration
V V Mp
Volume of water in water phase \ CT =C p +C w

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 Mass balance and solid-liquid partitioning (cont.) Mass balance and solid-liquid partitioning (cont.)

Now we can write mass balances for suspended solids, dissolved and
particulate fractions of contaminant. One implication of the solid-liquid
If we define the fraction of dissolved concentration, Fw, as partitioning is that a mass balance for suspended solids is needed, which
Cw Cw will allow us to determine how much contaminants will be transported
1
Fw = = = along with solids. Considering settling, sorption and volatilization, mass
CT ( K d Pw + 1)C w ( K d Pw + 1) balances can be written for Pw, Cp, and Cw, respectively, as
and the fraction of adsorbed concentration, Fp, as dM p æMp ö dM p dP dPw vs
= -v s Açç ÷÷ = -k sp M p Þ = V w = -v s APw Þ dt = - h Pw = -k sp Pw
Cp K d Cw Pw K d Pw dt è V ø dt dt
Fp = 1 - Fw = = = where ksp, is the
CT ( K d Pw + 1)Cw ( K d Pw + 1)
dC p (1) rate of settling, T-1.
V = -v s AC p dC
such that we can relate C w = Fw CT and C p = (1 - Fw )CT = Fp CT dt
Þ V T
= -k w ACw - vs AC p (3)
dt
Note that Fw and Fp are functions of contaminant’s partition dC w
V = - k w AC w (2) Note that equations (1) + (2) yields equation (3) with
coefficient Kd and suspended solid concentration Pw. dt dCT = d(Cp+Cw).

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Mass balance and solid-liquid partitioning (cont.) Mass balance and solid-liquid partitioning (cont.)

Also, note that the right hand side of the previous equation Under local equilibrium recognizing that Cw=FwCT and
(3) is not exculusively expressed in terms of dependent Cp=PwCads=FpCT, we obtain
variable (unknown) CT. That is, it also includes other
dCT
unknowns Cw and Cp. Consequently, the solution requires V = -k w AFwCT - vs AFp CT
dt
additional information on Cw and Cp.
When adsorption/desoprption kinetics are much faster than Here, notice that the adsorption and desorption terms
the other mass transfer reactions (i.e., settling and cancel upon summing the individual mass balances for Cw
volatilization), local equilibrium assumption (adsorption rate and Cp to obtain the above mass balance for CT.
= desorption rate) can be used to yield mass balance for CT.

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 Mass balance and solid-liquid partitioning (cont.) Mass balance and solid-liquid partitioning (cont.)

Note that both Freundlich and Langmuir isotherms exhibit

Cads
some linear behavior for low dissolved concentrations. This

Cads
is more consistent with the situation that concentrations of
most anthropogenic toxic contaminants are relatively low in
natural waters. Kd =
Cads
Cw
For such conditions adsorption becomes independent of
solid concentration and is driven only by dissolved Cw Cw
concentration. This situation also implies that the fraction of Linear part of Langmuir isotherm k de
k
Cw >> de
Cw << k ad
the contaminant in the dissolved and particulate form (i.e., at low concentrations k ad

Fw and Fp) remain constant. k ad amax Cads ® amax

Cads ® Cw ® K d Cw
k de
A Langmuir isotherm indicating asymptotes

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