Chapter 2 Adsorption

Adsorption on solid surfaces

Bond Chap 2
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IR > 2000 cm-1 1800 2000 cm-1

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3 fold 4 fold
site site

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GC Bond

G = H - TS

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rNi + rH = 0.125 + 0.035
= 0.16 nm

rNi + rNi,vdw + rH + rH,vdw

= 0.125 + 0.08 + 0.035 + 0.08
= 0.32 nm

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 p

A2

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Physically adsorbed molecule
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Endothermic chemisorption

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O2-
Ag

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Langmuir adsorption isotherm

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Assumptions of Langmuir adsorption isotherm :

1. The adsorbed species are held onto definite points of attachment

on the surface.
( This implies that the maximum adsorption possible corresponds
to a monolayer.)
Each site can accommodate only one adsorbed species.

2. The differential energy of adsorption is independent of surface

coverage.
(This implies that the surface is completely uniform so that there is
the same probability of adsorption on all sites.
A further implication is that adsorbed molecules are localized.)
Attraction or repulsion forces between adjacent adsorbed
molecules are taken to be negligible, so the energy of an adsorbed
species or the probability of adsorption onto an empty site are
independent of whether or not an adjacent site is occupied.

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Langmuir adsorption isotherm
K1
A + M A-M A: the adsorbed molecule -- adsorbate
K-1
p n(1-) n M: an adsorption site -- adsorbent
pressure Vacant sites
k: equilibrium constant
b: the adsorption coefficient of A
: fractional surface coverage; = V / Vm
Vm: the monolayer capacity

= X / Xmax; x is the amount adsorbed at a

given pressure and Xm is the maximum amount
that the surface can be taken up

= b = 1/p

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 1
2

T3 > T2 > T1
3

Adsorption is almost always exothermic, b must decrease with increase of temperature.

G Bond
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 V/P vs -V
Slop = 1/Vm

1/V vs 1/p

V =
Vm

Vm: the monolayer capacity

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Langmuir

Temkin

Freundlich

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 Adsorption of hydrogen
on evaporated film

Adsorption of CO

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 Langmuir
Brunauer,Emmett and Teller (BET)
microporous
solids

Brunauer,Emmett and Teller (BET) equation

Po : the saturated pressure of adsorbate at T

Xm ; monolayer capacity

Xm = 1/(I+S)

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Open-ended Open slit-shaped Open or closed pores
cylindrical pore capillaries of vaiousradius

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Hysteresis loop : evaporation of condensed gas in fine pores does not
occur as easily as its condensation; this is because
a molecule evaporating from a highly curved meniscus
has a higher probability of re-condensing than one
evaporating from a plane surface.

Lord Kelvin

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GC Bond
p25

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