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CML103-Week9-B

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6 views

CML103-Week9-B

Uploaded by

rohitmeena779201
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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DESORPTION

• A physical process where adsorbed atom are released from surface( reverse of
adsorption).
• This occurs when molecule gains enough energy to overcome the activation barrier
and binding energy that keep it attached to the surface.
• Desorption is always activated( Energy required to break chemical bonds)
• The average time that a molecule remains adsorbed on the surface is called Residence
time(τ) .
Let ,
Number of sites available = S
Number of sites occupied= S0
Number of sites available= S-S0
Depends on the partial pressure
Rate of adsorption= Ka[S-S0]PA
Rate of desorption= Kd[S0]

What does Kd physically mean?


Let’s dive in
RELATION BETWEEN Kd AND τ

Residence time equation Arrhenius type equation


τ: residence time
τ0 : pre exponential factor( also called vibrational
frequency factor)
Eads​: The adsorption activation energy.
R: The universal gas constant.
T: Temperature
PHYSICAL INTERPRETATION OF Kd

• Kd​ provides valuable information about


the binding affinity between an
adsorbate and a surface.
• Kd is inversely proportional to
residence time(τ )
• A lower Kd​ indicates stronger binding
and longer residence times.

• This relationship is fundamental in


understanding and designing processes Kd

involving adsorption and desorption in Inverse relationship between residence time


chemical engineering. and Kd has been shown
c stands for chemisorption
p stands for physisorption

The adsorbate needs to overcome a


Since the intersection point is –ve , thus no activation
barrier to be adsorbed.
energy is required.
Ea>0( as shown in the figure)
TEMPERATURE PROGRAMMED DESORPTION(TPD)

• A surface analysis techniques used to determine


desorption rates that were previously adsorbed on a
surface .
• We get desorption rates of each product species as a
function of Temperature of the surface . This is called
TPD spectra.
• As the temperature is known, it is possible to compute
the activation energy.

T=T0+ t
ADSORPTION ISOTHERM

• Adsorption Isotherm are usually


studied through graph known as
adsorption Isotherm .
• That is the amount of adsorbate
adsorbed on its adsorbent as a
function of its pressure at a constant
temperature.
Where,
X: Amount of adsorbate
M:weight of adsorbent
P: Pressure
.

LANGMUIR ADSORPTION ISOTHERM

• Langmuir hypothesised that a given surface has a


certain number of equivalent site (Ref. Fig1) to which a
species can stick either by physisorption or
chemisorption.
• A model that explains adsorption of adsorbate as an
ideal gas at constant temperature on a solid surface.
• According to this model, desorption and adsorption equivalent sites on solid surface,
are reversible process. occupied -(blue) unoccupied -(red)

• Adsorbate binding is treated as chemical reaction Fig 1

between adsorbate Ag (gas molecule ) and empty


sorption site S.
Mathematical form of Langmuir Isotherm
ASSUMPTIONS

• Monolayer Adsorption-Adsorption is limited to one layer of molecules, with no further adsorption on top of already adsorbed
molecules.
• Dynamic equilibrium: A dynamic equilibrium exists between adsorbed and desorbed molecules, meaning adsorption and desorption
rates are equal at equilibrium.
• Homogeneous surface: All adsorption sites are equivalent.
• No interaction between adsorbed molecules: Adsorbed molecules do not interact with each other
• Immobile adsorbates - Adsorbates are immobile on the surface of adsorbent.

Monolayer
Immobile
Homogenous Adsorbates
Surface

No
interaction
Dynamic between gas
Equilibrium molecule
DERIVATION OF LANGMUIR ADSORPTION ISOTHERM

1) Kinetic Method
A

b is only a constant if the enthalpy of


adsorption is independent of coverage

As with all chemical equilibria, the position of equilibrium


will depend upon a number of factors:
• The relative stabilities of the adsorbed and gas phase
species involved.
• The temperature of the system (both the gas and
surface, although these are normally the same).
• The pressure of the gas above the surface
2) Thermodynamic Method

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