Surfaces chemistry

Adsorption at solids
Solid: Adsorbent
Gas/Solute: Adsorbate

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 Outline
• Adsorption
• Comparison of physisorption and chemisorption
• The Langmuir treatment of adsorption
• Adsorption Kinetics
• Analytical Aspects Of Adsorption
• Other isotherms (BET, Freundlich)

• Texts: Introduction to colloids and Surface Chemistry – D.J. Shaw 2

• Physical Chemistry - Atkins
 Applications
• Central importance to many areas of pure and
applied research:

- Electronic device manufacture

- Heterogeneous catalysis
(e.g., Hydrogenation of alkenes, cracking of
crude oil over silica- alumina : zeolites)

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 Applications
- Wastewater treatment

- Environmental chemistry
(e.g. Leaching of pesticides in soil, chelation
of metal ions in humic acids)

- Chromatography

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 Adsorption
• Is the withdrawal of a substance from a bulk
phase (aqueous or solution) and its
accumulation at an interface.
• Strictly a surface phenomenon
• It is sometimes accompanied by deeper
penetration of the adsorbed substance into the
body (bulk) of a solid adsorbent, akin to the
formation of a solid solution – absorption
• The term Sorption covers both phenomena.
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• Non-Dissociative adsorption is said to occur when a molecule
adsorbs on to the surface from the gas phase without
fragmentation.

• When fragmentation does occur, the adsorption process is

termed dissociative.

• The free gas and the adsorbed gas are in dyanamic

equilibrium.

• Fractional coverage (ϴ )or extent of adsorption depends on : T,

P (gas) or conc. (solute) and on effective surface area.

• The variation of ϴ with pressure at a chosen temperature is

called the adsorption isotherm. 6
• Finely divided solids possess a very high SPECIFIC
SURFACE AREA (SSA) / m2g-1

• (activated C : ~ 1000 ; Si gel : ~ 500)

• Adsorption is spontaneous process, therefore (Gads )T , P  0

• (adsorption equilibrium if ) (Gads )T , P  0

• On the other hand, the adsorbed state is more “ordered” (2D vs 3D),
hence :
• Sads  0 (non-dissociative adsorption)(translational freedom
reduced)

Gads  H ads  TSads  0

• H ads  TSads  0 non-dissociative adsorption exothermic

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• Exception: Dissociative adsorption (e.g., H2
on glass 2 H(ads) )
Sads  0 , H  0
ads ,(endothermic adsorption), such that

Gads  0

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 Adsorption
Physical adsorption (physisorption)
 The bonding interaction between adsorbate and adsorbent is
long range but weak and is associated with van der Waals-type
interactions.
 The small Hads is insufficient to lead to bond breaking so
the physiosorbed molecule retains its identity, though it
might be distorted by the surface.

• Chemical adsorption (chemisorption)

 chemical bonds are formed between the molecules (atoms)
and the surface.

Note : both types of adsorption are exothermic

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 Comparison of physisorption and
chemisorption
Physisorption Chemisorption

Cause non-specific, long range Covalent/electrostatistic

(dispersion, forces) Van der forces, electron transfer
Waals forces
No electron Transfer
(redistribution of e- density)
Adsorbents All solid Some solids

Adsorbates All gases below the critical Some chemically reactive

point, intact molecules gases, dissociation into
atoms, ions, radicals
Temperature range Low temperatures Generally high temperatures

Heat of adsorption Low,~heat of condensation High, ~heat of reaction

(typical Hads ≈ - 20kJmol- (Hads ≈ - 200kJmol-
1), always exothermic 1)Exothermic

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 Comparison of physisorption and
chemisorption
Physisorption Chemisorption

Rate Very fast Strongly temp. dependent

Activation energy no barrier activation Generally high

barrier; Low (unactivated: low)
Surface Coverage multilayer monolayer

reversibility Highly reversible Often irrreversible

(adsorbate layer is always (C + O2(ads)
in eqm with molecules of CO, CO2 at high T)
gas phase)
Applications Determination of surface Determination of surface
area and pore size concentrations and
kinetics, rates of adsorption
and desorption,
determination of active
centres
Example N2 on C C6H6 on Pd 11
 Adsorption

Chemisorption Physisorption

Activated
- temperature sensitive
- varies according to a finite activation energy

Non-activated
rapid adsorption and near zero activation energy

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 ENERGETICS OF ADSORPTION

Adsorbate is diatom X2

X-X
X - X
d

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 Physisorption
Pure physisorption (e.g. Ar / metals ):

P.E. - the only attraction between the adsorbing

species and the surface arises from weak,
van der Waals forces.

-these forces give rise to a shallow minimum

in the PE curve at a relatively large distance
from the surface (typically d > 0.3 nm)
before the strong repulsive forces arising
d from electron density overlap cause a rapid
Ep increase in the total energy.

- there is no barrier to prevent the atom or

molecule which is approaching the surface
from entering this physisorption well, i.e. the
process is not activated and the kinetics of
physisorption are invariably fast.
d- distance from surface
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Dissociative (chemical) adsorption

X2 - D(X2)
X X
EP D(X2) – EC
EC – EP
X-X X X

Metal

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Kinetics of Desorption/ Adsorption
kd
• Xads Xdes
• kd / s-1 : desorption rate constant
• Arrhenius: kd = A exp(- Ed/RT)
• A ~ vibrational frequency
• Residence time ~ half-life

: average time between two successive

; attempts to escape from surface:

For Ed / kJ mol-1 = 25 t1/2 ~ 10-8 s (physisorption)

Ed / kJ mol-1 = 100 ~ 1 hr (chemisorption) 16
 Analytical Aspects Of Adsorption
• Quantitative measures of adsorption
# moles of adsorbate per gram of adsorbent : X / m (in mol g-1)

or, in the case of adsorption from the gas phase,

• adsorption volume (V) per gram of adsorbent, where : V = (nadsRT/P)/m
evaluated at STP (25oC, 1 atm), i.e. V = (nads x 22.4 dm3)/m
• V = V(T,P) gas solid
• X/m = X/m(T,c) solution solid

• X = Vsoln(cini – cfin) where; (cfin = c = equilibrium conc.)

• T constant: V(P) or X/m(c) : Recall:

relationship between the amount adsorbed (X) and the concentration (c) is
known as adsorption isotherm.
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18
 TYPE I ISOTHERMS: THE LANGMUIR MODEL

• Monolayer adsorption (Chemi/Physisorption)

V/cm3g-1

Vm

p/atm
Model assumptions:

1.Uniform surface with N equivalent adsorption sites per cm2

2. No interference of adsorbed particles with an adjacently adsorbed molecule
3. One molecule per site
4. Molar heat of adsorption H ads is the same for all sites and independent of
fractional coverage θ
5. No dissociation
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• Fractional coverage θ = Ns/N
= # sites occupied by adsorbate per cm2
total number of available adsorption sites
Can also be defined in terms of relative volumes and relative masses
θ =V = X
Vm Xm
(gas/solid) (solution/solid)
Kinetic scheme:
Y(g) + S(surface site) ka Y-S (associative adsorption)
kd
p 1–θ θ
• Equilibrium : rate of adsorption = rate of desorption
ka p (1 – θ) = kd θ
• (Adsorption from solution: replace p by c)
K p = θ / (1 – θ) adsorption constant (in atm-1 or M-1)
K(T) = ka / kd 21
  T , c  
Kp Kc
 (T , p)  Langmuir isotherm (T const.)
1  Kc
1  Kp

As p 0; θ = 0 p = gaseous partial pressure

when Kp << 1(low p) ; θ ~ Kp c = aqueous concentration
K= Langmuir equilibrium constant
when p ∞: θ 1
• In terms of adsorption volume:
Vm Kp 1 1 1 1
V   
1  Kp V Vm Vm K p
1/V

Vm = 1 / intercept
1/VmK
K = intercept / slope
1/Vm

1/p 22
Alternatively: p 1 p
 
V Vm K Vm

- Graph of p/V vs p has slope = 1/Vm, intercept = 1/VmK

m V Kp
 (T , p )   
m m Vm 1  Kp
hence mm = 1 / intercept
1 1 1 1
    K = intercept / slope
m mm mm K  p 
corresponding mass

• Vm and mm : total number of sites corresponding to a

monolayer

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 Dissociative adsorption
Y Y
Y Y Y Y

S S S S S S S S

ka
Y2 + 2 S k 2Y–S
d
p 1–θ θ
Adsorption equilibrium
ka p (1 – θ)2 = kd θ2

  
2
Thus: Kp   
1 
from which we obtain: (K = K(T))
Kp
 (T , p) 
1  Kp 24
• with θ = V/Vm (V = adsorption volume of Y2 at STP) this can
be reorganised to:

1 1 1 1
  
V Vm Vm K p

1/V Vm = 1 / intercept;

1/Vm√K K = (intercept / slope)2

1/Vm

OR 1/√p

where:
Vm = 1 / slope;
p 1 1
   p
V Vm K Vm K = (slope / intercept)2
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 Limitations to Langmuir Model
• Does not explain multi-layer adsorption and limited
to low pressure studies.
• ∆Hads is not independent of coverage:
- also on a real surface some sites are better so gas
molecules search for these first and ∆Hads is greater
for better sites.
- as molecules of adsorbate pack closer on the surface
with increasing coverage, inevitably some lateral
interactions will result, which will change ∆Hads.

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MULTILAYER ADSORPTION – BET Model

• Model assumptions:
(1) smooth, uniform surface
(2) same number of adsorbate molecules in each layer
when full
(3) no lateral interactions
(4) H ads,1  H ads, 2  H ads,3  ...  H vap (heat of adsorption
is same for each layer except layer 1)
(5) dynamic equilibrium between adjacent layers
(6) non-dissociative adsorption
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4
3
2
1

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• Coverage : θ = V / Vm
• Vm = adsorption volume (STP) occupied by molecules
covering a monolayer (so θ may now become > 1!)
• 2 equilibrium constants:
k a(1)  
K1 (T )  (1)  1 2
kd (1  1 ) p

• K2(T) defined analogously for layers 2, 3,…

• Define :
• C is BET constant
c(T )  K1(T ) / K2 (T )

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• so that :
d ln c d ln K1 d ln K 2
 
d (1/ T ) d (1/ T ) d (1/ T )

H ads ,1 H vap
 
R R
 H ads ,1  H vap 
 c(T )  exp 
 RT 
• Chemisorption in layer # 1
H ads ,1  H vap  0
(type II isotherms)
c(T) decreases with increasing T
• Define : z = p / p0 ( p and p0 = equilibrium and saturated
vapour pressure of adsorbate at temperature T respectively)
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 V cz
 Brunauer-Emmett-Teller (BET) isotherm
Vm (1  z )(1  (c  1) z )

• contains 2 parameters : Vm and c(T)

• Linearised form (multiply both sides by and invert):
z 1 c 1
  z
(1  z )V cVm cVm

z T
(1  z )V
c 1
cVm
1
cVm

z
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• Vm = 1 / (slope + intercept) # adsorption sites
• c(T) = 1 + (slope / intercept) H ads,1
• Vm allows us to calculate an effective surface area of substrate.

• Determination of specific surface area

• SSA = adsorbent area / adsorbent mass
• = NA nmax a / m
= NA Vm a / (22.4 dm3 m)
• NA = 6.0 x 1023 mol-1 ;
a = area of one adsorbate molecule
Vm = volume corresponding to one monolayer
nmax total number of moles corresponding to one
monolayer
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