ADSORPTION

LIA LAILA, S.FARM., M.SC., APT.

PHARMACEUTICAL TECHNOLOGY DEPARTMENT
FACULTY OF PHARMACY
UNIVERSITY OF SUMATERA UTARA
ADSORPTION IS THE PROCESS THROUGH
WHICH A SUBSTANCE, ORIGINALLY
PRESENT IN ONE PHASE, IS REMOVED
FROM THAT PHASE BY ACCUMULATION AT
THE INTERFACE BETWEEN THAT PHASE
AND A SEPARATE (SOLID) PHASE.
ADSORBENT, ADSORPT DAN
ADSORBATE
 TYPE OF ADSORPTION
• PHYSICAL ADSORPTION (PHYSISORPTION) → ABSENCE OF
CHEMICAL BONDS THE MOLECULE RETAINS ITS GAS PHASE
ELECTRONIC STRUCTURE, ALTHOUGH SOME DISTORTION IS
STILL POSSIBLE.
THE FORCES OF ATTRACTION EXISTING BETWEEN ADSORBATE
AND ADSORBENT ARE WEAK VANDERWAALS
FORCES OF ATTRACTION.

• CHEMICAL ADSORPTION (CHEMISORPTION) → STRONGER

PERTURBATION OF THE MOLECULAR ELECTRONIC STRUCTURE
WITH FORMATION OF CHEMICAL BONDS WITH THE SUBSTRATE.
THE FORCE OF ATTRACTION EXISTING BETWEEN ADSORBATE
AND ADSORBENT ARE CHEMICAL FORCES OF
ATTRACTION OR CHEMICAL BOND.
 FACTORS AFFECTING
ADSORPTION
THE MOST IMPORTANT FACTORS AFFECTING ADSORPTION ARE:
• SURFACE AREA OF ADSORBENT.
LARGER SIZES IMPLY A GREATER ADSORPTION CAPACITY.
• PARTICLE SIZE OF ADSORBENT.
SMALLER PARTICLE SIZES REDUCE INTERNAL DIFFUSIONAL AND
MASS TRANSFER LIMITATION TO THE PENETRATION OF THE
ADSORBATE INSIDE THE ADSORBENT (I.E., EQUILIBRIUM IS MORE
EASILY ACHIEVED AND NEARLY FULL ADSORPTION CAPABILITY CAN
BE ATTAINED). HOWEVER, WASTEWATER DROP ACROSS COLUMNS
PACKED WITH POWDERED MATERIAL IS TOO HIGH FOR USE OF THIS
MATERIAL IN PACKED BEDS. ADDITION OF POWDERED ADSORBENT
MUST BE FOLLOWED BY THEIR REMOVAL.
• CONTACT TIME OR RESIDENCE TIME.
THE LONGER THE TIME THE MORE COMPLETE THE
ADSORPTION WILL BE. HOWEVER, THE EQUIPMENT WILL BE
LARGER.
• SOLUBILITY OF SOLUTE (ADSORBATE) IN LIQUID
SUBSTANCES SLIGHTLY SOLUBLE IN WATER WILL BE MORE
EASILY REMOVED FROM WATER (I.E., ADSORBED) THAN
SUBSTANCES WITH HIGH SOLUBILITY. ALSO, NON-POLAR
SUBSTANCES WILL BE MORE EASILY REMOVED THAN POLAR
SUBSTANCES SINCE THE LATTER HAVE A GREATER AFFINITY
FOR WATER.
• AFFINITY OF THE SOLUTE FOR THE ADSORBENT (CARBON).
THE SURFACE OF ACTIVATED CARBON IS ONLY SLIGHTLY
POLAR. HENCE NON-POLAR SUBSTANCES WILL BE MORE
EASILY PICKED UP BY THE CARBON THAN POLAR ONES.
• NUMBER OF CARBON ATOMS.
FOR SUBSTANCES IN THE SAME HOMOLOGOUS SERIES A
LARGER NUMBER OF CARBON ATOMS IS GENERALLY
ASSOCIATED WITH A LOWER POLARITY AND HENCE A
GREATER POTENTIAL FOR BEING ADSORBED (E.G., THE
DEGREE OF ADSORPTION INCREASES IN THE SEQUENCE
FORMIC-ACETICPROPIONIC-BUTYRIC ACID).
• SIZE OF THE MOLECULE WITH RESPECT TO SIZE OF THE
PORES.
LARGE MOLECULES MAY BE TOO LARGE TO ENTER SMALL
PORES. THIS MAY REDUCE ADSORPTION INDEPENDENTLY OF
OTHER CAUSES.
• DEGREE OF IONIZATION OF THE ADSORBATE MOLECULE.
MORE HIGHLY IONIZED MOLECULES ARE ADSORBED TO A
SMALLER DEGREE THAN NEUTRAL MOLECULES.
• PH.
THE DEGREE OF IONIZATION OF A SPECIES IS AFFECTED BY
THE PH (E.G., A WEAK ACID OR A WEAK BASIS). THIS, IN
TURN, AFFECTS ADSORPTION.
 ADSORPTION ISOTHERM
• ADSORPTION IS THE AMOUNT OF ADSORBATE ON THE ADSORBENT
AS A FUNCTION IF ITS PRESSURE OR CONCENTRATION AT CONSTANT
TEMPERATURE

• THE ADSORPTION EQUILIBRIUM RELATES Q TO C. THE EQUILIBRIUM IS A

FUNCTION OF THE TEMPERATURE. THEREFORE, THE ADSORPTION
EQUILIBRIUM RELATIONSHIP AT A GIVEN TEMPERATURE IS TYPICALLY
REFERRED TO AS ADSORPTION ISOTHERM, I.E.:
Q = F (C)
WHERE:
• Q = MASS OF SPECIES ADSORBED/MASS OF ADSORBENT (I.E.,
EQUILIBRIUM CONCENTRATION OF ADSORBABLE SPECIES IN SOLID
ADSORBENT)
• C = EQUILIBRIUM CONCENTRATION OF ADSORBABLE SPECIES IN
SOLUTION
 TYPES OF ADSORPTION
ISOTHERMS
• DIFFERENT ADSORBATES-ADSORBENTS EXHIBIT
DIFFERENT TYPES OF EQUILIBRIUM RELATIONSHIPS (I.E., THE
FUNCTION Q = F(C) MAY TAKE DIFFERENT MATHEMATICAL
FORMS)
• IT HAS BEEN FOUND THAT FOR MOST OF THE CASES OF
IMPORTANCE IN WASTEWATER TREATMENT THE FUNCTION Q
= F(C) TAKES THE FORM OF ONE OF THE FOLLOWING
ISOTHERMS:
• - LANGMUIR ISOTHERM
• - BRAUNER-EMMET-TELLER (BET) ISOTHERM
• - FREUNDLICH ISOTHERM
ADSORPTION MODEL FOR LANGMUIR
ISOTHERM

THE ASSUMPTIONS MADE IN THE DERIVATION OF THE LANGMUIR MODEL

ARE:
• ADSORPTION IS A REVERSIBLE PROCESS
• THE ADSORBED LAYER IS MADE UP OF A SINGLE LAYER OF
MOLECULES
• THE ADSORBED MOLECULES DO NOT MOVE ON THE SURFACE OF THE
ADSORBENT. HOWEVER, THEY CAN BE LOST BACK TO THE SOLUTION
• THE ENTHALPY OF ADSORPTION IS THE SAME FOR ALL
• MOLECULES INDEPENDENTLY OF HOW MANY HAVE BEEN ADSORBED
SCHEMATIC OF LANGMUIR
ADSORPTION MODEL
 DERIVATION OF LANGMUIR ISOTHERM

• IN THE LANGMUIR MODEL (1918) ADSORPTION IS ASSUMED

TO BE A DYNAMIC PROCESS. AT EQUILIBRIUM THE NUMBER
OF MOLECULES BEING ADSORBED WILL BE EQUAL TO THE
NUMBER OF MOLECULES LEAVING THE ADSORBED STATE,
I.E.:
DERIVATION OF LANGMUIR
ISOTHERM
SCHEMATIC OF BET ADSORPTION
MODEL
Log q

Log C
SURFACE CHEMICAL REACTIONS
• (A) CORROSION REACTIONS
• IN CORROSION, ADSORBATES REACT DIRECTLY WITH THE SUBSTRATE
ATOMS TO FORM NEW CHEMICAL SPECIES. THE PRODUCTS MAY DESORB
FROM THE SURFACE (VOLATILIZATION REACTION) OR MAY REMAIN
ADSORBED IN FORMING A CORROSION LAYER. CORROSION REACTIONS
HAVE MANY INDUSTRIAL APPLICATIONS, SUCH AS DRY ETCHING OF
SEMICONDUCTOR SURFACES.
• AN EXAMPLE OF A VOLATILIZATION REACTION IS THE ETCHING OF SI BY
FLUORINE. IN THIS CASE, FLUORINE REACTS WITH THE SI SURFACE TO
FORM SIF4 GAS. NOTE THAT THE CRYSTALLINITY OF THE REMAINING
SURFACE IS ALSO SEVERELY DISRUPTED BY THIS REACTION.
• AN EXAMPLE OF CORROSION LAYER FORMATION IS THE OXIDATION OF
FE METAL TO FORM RUST. IN THIS CASE, NONE OF THE PRODUCTS ARE
VOLATILE, BUT THE CRYSTALLINITY OF THE SURFACE IS DISRUPTED AS
THE BULK OXIDE FORMS.
• (B) CRYSTAL GROWTH REACTIONS
• THE GROWTH OF SOLID FILMS ONTO SOLID SUBSTRATES
ALLOWS FOR THE PRODUCTION OF ARTIFICIAL STRUCTURES
THAT CAN BE USED FOR MANY PURPOSES.
• FOR EXAMPLE, FILM GROWTH IS USED TO CREATE PN
JUNCTIONS AND METAL–SEMICONDUCTOR CONTACTS
DURING SEMICONDUCTOR MANUFACTURE, AND TO
PRODUCE CATALYTIC SURFACES WITH PROPERTIES THAT
ARE NOT FOUND IN ANY SINGLE MATERIAL.
• LUBRICATION CAN BE APPLIED TO SOLID SURFACES BY THE
APPROPRIATE GROWTH OF A SOLID LUBRICATING FILM.
• FILM GROWTH IS ALSO USED TO FABRICATE QUANTUM-
WELLS AND OTHER TYPES OF LAYERED STRUCTURES THAT
HAVE UNIQUE ELECTRONIC PROPERTIES.
• THE THREE BASIC TYPES OF FILM GROWTH REACTIONS ARE:
A. PHYSICAL VAPOUR DEPOSITION (PVD)
IN PVD, AN ATOMIC GAS IS CONDENSED ONTO A SURFACE
FORMING A SOLID.
B. CHEMICAL VAPOUR DEPOSITION (CVD)
IN CVD, A MOLECULAR GAS DISSOCIATES UPON
ADSORPTION. SOME OF THE DISSOCIATION FRAGMENTS
SOLIDIFY TO FORM THE MATERIAL, WHILE OTHER
DISSOCIATION FRAGMENTS ARE EVOLVED BACK INTO THE
GAS PHASE.
C. MOLECULAR BEAM EPITAXY (MBE)
IN MBE, CAREFULLY CONTROLLED ATOMIC AND/OR
MOLECULAR BEAMS ARE CONDENSED ONTO A SURFACE IN
THE PROPER STOICHIOMETRY IN ORDER TO GROW A
DESIRED MATERIAL
(C) CATALYTIC REACTIONS
IN A CATALYTIC REACTION, THE REACTANTS FIRST
ADSORB ONTO THE SURFACE AND THEN REACT WITH
EACH OTHER TO FORM VOLATILE PRODUCT(S). THE
SUBSTRATE ITSELF IS NOT AFFECTED BY THE REACTION,
BUT THE REACTION WOULD NOT OCCUR WITHOUT ITS
PRESENCE.
• TYPES OF CATALYTIC REACTIONS INCLUDE EXCHANGE,
RECOMBINATION (EX: DNA BINDING), UNIMOLECULAR
DECOMPOSITION (EX: FORMIC ACID ON TIO2), AND
BIMOLECULAR REACTIONS (EX: CARBOXYLIC ACIDS ON
OXIDES).
 LATIHAN

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