Syahrul SSKM 3-Surface Characterization

Surface Characterization
Syahrul Khairi, 21 Oktober 2015

Introduction
Surface Chemistry
 80 % of all important chemical reactions take place on interfaces
 Catalytic processes is the largest chemical industry
 Energy technology, fuel cell, splitting of water by solar
 Environtmental science
 Semiconductor technology
 Biosurface
Introduction
Elementary surface reaction
Three pore size regimes
Pore diameter (nm)
Microporous <2
Mesoporous 2 ~ 50
Macroporous > 50
Distinctions arise from differences in how

adsorbates physisorb.
 Adsorptive: Substance
that is capable of being
adsorbed as it exists in
the fluid state
 Adsorbate: material in
adsorbed state
 Adsorbent: surface of
the solid on which
adsorption occure
Physisorption vs. Chemisorption
Weak attraction produced  Strong attraction of
by induced dipole, van der adsorbate to surface due to
waals force sharing of electron
Easly reversible (desorbed)  Not easly reversible
Adsorbent surface not  Surface often altered

usually altered
 Example: poisoning of H2S
Example: H2O on Co or Fe sites on FT
condensation on cold glass catalyst
Ideal vs. actual physisorption behavior
N2 is most commonly used adsorbate because:
 N2 has permanent quadrupole moment (responsible for
forming well-defined monolayer on most surfaces )
 Level of specivity on most surfaces not too strong for N2
 Liquid and gaseous N2 are readily available and cheap

The most common adsorbate used is Nitrogen, however,
other adsorbates are used in some circumstances
Molecular
Temp Cross Sectional Area
GAS weight
(K) (nm2)
(g/mol)
Ar 77.35 0.142 39.948
87.27
CO2 195 0.195 44.01
273
298
CO 90 0.163 28.01
N2 77.35 0.162 28.0134
90
O2 90
C4H10 273 0.469 58.12
298
 Small certain amount of sample
to be analyzed is placed in clean,
dry sample tube
 Sample tube is degassed to

remove moisture and other
contaminants (flow dry N2 over
sample, heated to > 100 oC ip to
400 oC
 Evacuated to near vacuum and

immersed in N2 bath @ 77K
 N2 gas introduced to small tubes

in small increments; volume gas
added and equilibrium pressure
recorded
Nova Quantachrome 4200e
Results obtained plotted as isotherm
P0 is saturation pressure of N2 (ambient press)

Different isotherm shapes possible
Type I isotherm
 Indicates sample contains
micropore only
 Sometimes a narrow
hysteresis is observed
 Observed in:
o Charcoal
o Silica
o Molecular sieves
o Stannic oxide gel
o Ammonium
phosphomolibdate
Type I isotherm
 The fraction of the surface sites occupied by adsorbed A molecules is

denoted by 
 The adsorption process is assumed to be an elementary process so
that the rate of adsorption is first order in the concentration of A in
the fluid phase and is also proportional to 1-.
Rate of adsorption = k1[A](1- )

Rate of desorption = k1` 
 At equilibrium, the rate of desorption equals the rate of adsorption

k1[A](1- ) = k1` 
 Langmuir isotherm:
Type I isotherm
Theory predict fit to Langmuir isotherm
p = pressure
B = constant at given temperature
zm = molecules adsorbed per cm2 in completed monolayer
v1 = oscillation frequency of adsorbed molecules
E1 = energy of desorption
Introduction
Type IV isotherm
 Porous type IV analogous

to non-porous type II
 Hysteresis is observed
 Type IV appears in solids

that possess mesopores
(2-50 nm
Introduction
Determining surface area of adsorbent
 If total amount of adsorbate taken up by adsorbent at

monolayer coverage is known, total surface area of
adsorbent can be calculated
 Area of N2 molecule = 0.162 nm2

BET
• Brunauer, Emmett and Teller (BET), most common
method used to describe specific surface area:
The BET equation –
W= weight of gas adsorbed

P/P0 =relative pressure
Wm = weight of adsorbate as monolayer
C = BET constant
Adsorption-Desorption
Adsorption 1
Adsorption 2
Adsorption 3
Adsorption 4
Adsorption 5
Adsorption 6
Adsorption 7; Pores filled

Desorption 1
Desorption 2
Desorption 3
Desorption 4
Desorption 5; Adsorbate removed

Type IV isotherm
Form of type IV isotherm
Open-ended cylindrical Capillary space between Tubular or ink-bottle

pores lying in narrow parallel plates or open pores of varying radius
range of radius slit-shaped capillaries (e.g. Pores with
restrictions)
 During adsorption, meniscus
not formed between parallel
plates until vapor pressure
reaches saturation
 Upon desorption, cylindrical

meniscus is present between
plates, which gradually come
together as liquid evaporates
(horizontal part of
desorption curve, A) Capillary space between
parallel plates or open
slit-shaped capillaries
 Adsorption, (1) Pore radius rn
begin to fill first
corresponding with p/p0
ratio in Kelvin equation. (2)
Pore continue to fill as p/p0
increases, the meniscus
gradually increasing in radius
 Desorption, (1) Pore should

fail to empty, A , until Tubular or ink-bottle
pressure falls to value pores of varying radius
(e.g. Pores with
corresponding to rn. (2) At B, restrictions)
all pore empty at once.
Other Methods
 Barrett-Joyner-Halenda Method (BJH)
 Dollimore Heal Method (DH)
 Alpha S Method (αs)
 MP Method (MP)
 Dubinn-Radushkevic Method (DR)
 Dubinin-Astakhov Method (DA)
 Horvath-Kawazoe Method (HK)
 Saito-Foley Method (SF)
 Density Functional Theory Method (DFT)
 Frenkel-Halsey-Hill Method (FHH)
 Neimark-Kiselev Method (NK)
Gas sorption calculation methods
p/p0 range model Mechanism Calculation
1x10-7 to 0.02 Micropore filling DFT, GCMC, HK, SF, DA, DR
0.01 to 0.1 Sub-monolayer formation DR
0.05 to 0.3 Monolayer complete BET, Langmuir
> 0.1 Multilayer formation t-plot (de-Boer, FHH)
< 0.35 Capillary condensation BJH, DH
Capillary filling in
0.1 to 0.5 DFT, BJH
M41S-types materials
Different theories of physisorption
Surface area Pore volume Pore size
BET Total pore volume DR average
Langmuir t-plot (micropore volume) BJH
DR DR (micropore volume) DH
MP and t-plot DA DFT
αs-plot BJH HK
BJH DFT SF
DH DH
DFT
C Constant
• Relative error between
single and multipoint
BET, (typically measured
at P/P0 of 0.3)

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Surface Characterization

Syahrul Khairi, 21 Oktober 2015

Pore diameter (nm)

Distinctions arise from differences in how

Easly reversible (desorbed)  Not easly reversible

Adsorbent surface not  Surface often altered

 Level of specivity on most surfaces not too strong for N2

 Liquid and gaseous N2 are readily available and cheap

 Sample tube is degassed to

 Evacuated to near vacuum and

 N2 gas introduced to small tubes

P0 is saturation pressure of N2 (ambient press)

 The fraction of the surface sites occupied by adsorbed A molecules is

Rate of adsorption = k1[A](1- )

 At equilibrium, the rate of desorption equals the rate of adsorption

 Porous type IV analogous

 Type IV appears in solids

Determining surface area of adsorbent

 If total amount of adsorbate taken up by adsorbent at

 Area of N2 molecule = 0.162 nm2

W= weight of gas adsorbed

Adsorption 7; Pores filled

Desorption 5; Adsorbate removed

Open-ended cylindrical Capillary space between Tubular or ink-bottle

 Upon desorption, cylindrical

 Desorption, (1) Pore should

p/p0 range model Mechanism Calculation

1x10-7 to 0.02 Micropore filling DFT, GCMC, HK, SF, DA, DR

0.01 to 0.1 Sub-monolayer formation DR

0.05 to 0.3 Monolayer complete BET, Langmuir

> 0.1 Multilayer formation t-plot (de-Boer, FHH)

< 0.35 Capillary condensation BJH, DH

BET Total pore volume DR average

Langmuir t-plot (micropore volume) BJH

MP and t-plot DA DFT

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