UNIT 3:SURFACES

CHEMISTRY
ADSORPTION AT SOLIDS
SOLID: ADSORBENT
GAS/SOLUTE: ADSORBATE

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 OUTLINE
AT THE END OF THE UNIT, STUDENTS SHOULD BE ABLE TO:
Distinguish between absorption and adsorption and derive
expressions for adsorption isotherm
Distinguish between monolayer and heterolayer adsorption
Distinguish between physical adsorption and chemical adsorption
Understand the theory and application of surface activity
surfactants and their technical application
Understand the theory and application of colloids, adhesives,
foams and emulsions

•TEXTS: INTRODUCTION TO COLLOIDS AND SURFACE CHEMISTRY – D.J.

SHAW
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•ELEMENTS OF 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
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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 ADSORPTION

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
 ADSORPTION
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

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 ADSORPTION
On the other hand, the adsorbed state is more “ordered”, hence:

S ads  0 (non-dissociative adsorption… translational freedom

reduced)
Gads H ads  TS ads  0

H ads  TS ads  0
 Non-dissociative adsorption exothermic

Exception: dissociative adsorption (e.g: H2 on glass 2 H(ads) )

S ads  0 H ads  0 Gads  0
 , ,(endothermic adsorption), such that

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 TYPES OF 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 enthalpy change (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 (adsorbent).

Both types of adsorption

are exothermic 9
 COMPARISON OF PHYSISORPTION AND
CHEMISORPTION
Physisorption Chemisorption

Cause Non-specific, long range Covalent/electrostatistic forces,

(dispersion, forces) van der 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 gases,
point, intact molecules dissociation into atoms, ions,
radicals
Temperature range Low temperatures Generally high temperatures

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

(typical ads ≈ - 20kJmol-1), (ads ≈ - 200kJmol-1)
always exothermic Exothermic
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COMPARISON OF PHYSISORPTION AND
CHEMISORPTION
Physisorption Chemisorption

Rate Very fast Strongly temp. dependent

Activation energy no barrier activation barrier; Generally high (unactivated:

Low low)
Surface Coverage multilayer monolayer

Reversibility Highly reversible (adsorbate Often irrreversible

layer is always in equilibrium (C + O2(ads) CO, CO2
with molecules of gas phase) at high T)

Applications Determination of surface area Determination of surface

and pore size concentrations and kinetics,
rates of adsorption and
desorption, determination of
active centres
Example Gas particle on charcoal (N2 C6H6 on Pd, O2 on Fe
on C), dust particle on the 11
skin
 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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 PHYSISORPTION
Adsorbate is diatom X2 Pure physisorption (e.g. Ar / metals ):

X-X these weak forces give rise to a shallow

X - X
d minimum in the PE curve at a relatively
P.E. large distance from the surface (typically d >
0.3 nm) before the strong repulsive forces
arising from electron density overlap cause a
rapid 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
d process is not activated and the kinetics of
Ep physisorption are invariably fast.

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d- distance from surface
DISSOCIATIVE (CHEMICAL) ADSORPTION

X2 X X

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 / kJmol-1 = 25 t1/2 ~ 10-8 s (physisorption) 15

Ed / kJ mol-1 = 100 ~ 1 hr (chemisorption)

 POLL #1

• At the equilibrium position in the process of

adsorption ____.
a. ∆H > 0
b.∆H > T∆S
c. ∆H = T∆S
d.∆H < T∆S

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 POLL #2

• Extent of physisorption of a gas increase with ______.

a.increase in temperature
b.decrease in surface area of adsorbent
c.decrease in temperature
d.decrease in strength of van der Waal forces

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 POLL #3

• Which of the following is not applicable to the

phenomenon of adsorption?

a. ∆H > 0
b. ∆S < 0
c. ∆G < 0
d. ∆H < 0

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 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

The relationship between the amount adsorbate (X) and the

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concentration (c) is known as adsorption isotherm.
 TYPE I ISOTHERMS: THE LANGMUIR
MODEL

Monolayer adsorption
Model assumptions:
(chemi/physisorption)
1.Uniform surface with N
V/cm3g-1 equivalent adsorption sites per
cm2
Vm 2. No interference of adsorbed
particles with an adjacently
adsorbed molecule
3. One molecule per site
p/atm 4. Molar heat of adsorption, H ads
is the same for all sites and
independent of fractional
coverage θ 20

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 / Vm = X / Xm

(Gas/solid) (solution/solid)
Kinetic scheme:
ka
Y(g) + S(surface site) 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)
 Kp = θ / (1 – θ) adsorption constant (in atm-1 or M-1) 22

 K(T) = ka / kd
 Kc
 (T , p ) 
Kp Langmuir isotherm (T const.)  T , c  
1  Kp 1  Kc

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

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

Vm = 1 / intercept
1/VmK
K = intercept / slope
1/Vm
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1/p
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
1 1 1 1 mm = 1 / intercept
   
m mm mm K  p 
K = intercept / slope
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 2Y–S
kd
p 1–θ θ
Adsorption equilibrium
ka p (1 – θ)2 = kd θ2
2
Thus: Kp   
 
 1   
Kp
 (T , p ) 
From which we obtain: 1  Kp(K = K(T)) 25
• With θ = V/Vm (V = adsorption volume of Y2 at STP) this can be reorganized
to:
1 1 1 1
  
V Vm Vm K p

1/V Vm = 1 / intercept;

1/Vm√K K = (intercept / slope)2

1/Vm

1/√p

OR Where,
p 1 1
   p
V Vm K Vm Vm = 1 / slope; 26
K = (slope / intercept)2
 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,…

c(T ) K1 (T ) / K 2 (T )
• Define :
• C is BET constant
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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 pressure30of
adsorbate at temperature T respectively)
 Brunauer-Emmett-Teller (BET) isotherm
V cz

Vm (1  z )(1  (c  1) z )

• Contains 2 parameters : vm and c(t)

• Linearized 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
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z
• 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 32
 SURFACE ACTIVITY
SURFACTANT
• Surfactants are substances that preferentially
accumulate at the boundary (interface)
between two phases.
• This adsorption at the various interfaces
existing between solid, liquid and gases causes
a change in the nature of the interfaces. Thus:
• Lowering the interfacial tension between oil and
water phases facilitate emulsion formation
• The adsorption of surfactants on insoluble particles
enables the dispersion of particles to form suspension
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