Surface Area and Porosity

Susi Nurul Khalifah

Why Studying Surface Area and Porosity?

Just like particle size and shape, surface area and

porosity are key physical parameters that highly
determine the performance and behavior of solids
and powders
Why Studying Porosity
 How to obtain surface area / porosity?
Particle dimensions allow calculation of specific surface area

m2/g

What if… porosity is present

Porosity can be present on different length scales
• sub-nanometer – micrometer scale
and … by different features
• Inter-particle porosity
• Intra-particle porosity
Pore size and shape selectivity
Classification of Porosity
Classification of Porosity
Physical Adsorption
 Gas Adsorption Definitions
 Adsorbent
Solid material that can adsorb gas molecules
 Adsorptive
Gas that can be adsorbed
 Adsorbate
Gas that already has been adsorbed
 Physical gas adsorption (Physisorption)
Adsorption by weak interactions (Vanderwaals
interactions)
 Chemical gas adsorption (Chemisorption)
Adsorption by strong interactions (chemical bonds)
 Adsorption

• Quantity adsorbed - always normalized for mass - cm3/g or

moles/g

•Relative pressure - equilibrium pressure divided by saturation

pressure - p/po
o Equilibrium pressure - vapor pressure above the sample corrected
for temperature (thermal transpiration)
o Saturation pressure - vapor pressure above a liquid

•Surface energy - solid/fluid interaction, strength, and

heterogeneity
 Sample Preparation
 Clean the surface
- Surface and pores free for adsorptive
- Preventing undesirable desorption of guest species during analysis
(unreliable results)
 Remove volatiles
• Water
• CO2
• Solvents
 Controlled environment!
• Inert purge or vacuum
• Temperature control
 Avoid Phase Changes
 Cleaning procedure

 Elevated temperature to desorb gas and vapor molecules

(be aware of phase transitions / sintering)
 Vacuum (or flowing gas) to remove the desorbed
molecules
 Physical Adsorption
 Molecules from the gas phase strike the
surface.
 At equilibrium the molecule adsorbs, lose the
heat of adsorption, and subsequently desorb
from surface.
 At equilibrium the rate of condensation = the
rate of desorption
 Constant surface coverage at equilibrium.
 Surface features change the adsorption
potential.
 Surface area models neglect the effects of
localized phenomenon.
 Curve surfaces or roughness provide
enhanced adsorption potential.
 Physical Adsorption
 Not activated (no barrier)
 Rapid
 Weak (< 38 kJ/mol)
 Atomic/Molecular
 Reversible
 Non-specific
 May form multilayers
 van der Waals/dipole
interactions
 Often measured near the
condensation temperature
 Chemical Adsorption

 May be activated
 Covalent, metallic, ionic
 Strong (> 35 kJ/mol)
 May be dissociative
 Often irreversible
 Specific - surface
symmetry
 Limited to a monolayer
 Wide temperature range
Isotherm Types
 Tipe I
Tipe ini khas untuk terjadi untuk fisisorpsi gas pada padatan mikropori dan
kemisorpsi isotermal.
 Tipe II
Tipe ini biasanya terlihat dari adsorpsi pada padatan non pori.
 Tipe III
Grafik ini khas untuk uap, misalnya air pada padatan hidrofobik.
 Tipe IV
Grafik Tipe IV ini memperlihatkan loop histerisis yang disebabkan oleh
kondensasikapiler dalam mesopori. Jadi tipe IV ini khas untuk material mesopori.
 Tipe V
Grafik ini juga khas untuk uap seperti halnya Tipe III, tetapi terlihat adanya loop
histerisis yang juga disebabkan oleh kondensasi kapiler pada mesopori.
 Tipe VI
Grafik isotermal seperti anak tangga, biasanya terlihat untuk adsorpsi nitrogen
pada karbon tertentu.
Micropores
Non-pores
Mesopores

capillary
condensation in
mesopores
Adsorptives

 Nitrogen
 Argon
 Krypton
 Nitrogen

 Broad usage Limitations

• Surface area • Strong interactions
• t-plot • Slow diffusion < 0.5 nm
pores
• Pore size distributions
• Reduced precision for
- BJH - bulk fluid materials with <1m2/g
properties (10µmol/g monolayer)
- NLDFT – excess
density
 Argon
 Pore size distributions Limitations
• H-K calculations • Ar molecular area not a
• NLDFT – excess density generally accepted value
• Statistical t-curves based
 Benefits
upon N2
• Reduced interaction • Not used for BJH - bulk fluid
compared to N2 methods
• Molecular size < N2 and
faster diffusion dueto size
and T (87K)
Y zeolite, Ar Adsorption
ZSM-5, Ar Adsorption
 Krypton

 Surface area estimates BET Limitations

• Low specific surface area •Pressure range limited to < 1
(< 1m2/g) torr at 77 K (<0.3 p/po)
• Low absolute area limited •General agreement with N2
sample quantity •Cost
•Limited to surface area
 Benefits
applications
• High precision, low pressure
analysis
Surface Area