ADSORPTION

FAR 221/3

Department of Pharmacy
Island College of Technology
2007

Objectives

Students should comprehend and understand and explain matters relating to this topic
namely;

- Surface and interfacial tensions, together with the Gibbs free energies related to them
- Process of adsorption through the formation of bonds
- The different types of gas adsorption isotherms;
 Freundlich
 Langmuir
 Brunauer, Emmet, Teller (BET)
- Determination or prediction of various physicochemical phenomena based on
adsorption studies.

Factors affecting gas adsorption

- Adsorption of dissolved solutes on solids
- Different types of disolved solutes adsorption isotherms;
 Langmuir
 Constant
 High affinity
 Slow
- Information gleaned from the adsorption of solutes onto the surfaces of solids.
- Factors affecting the dissolved solute adsorption

Contents and Instructions

SURFACE FREE ENERGY AND ADSORPTION

• Recap briefly the relationships between free energy, surface area and surface
tension
• Describe the difference in free energy between the surface of a solid and the bulk
• Describe the process that occurs at the interfaces of solid-air, solid-liquid and
solid-solid, including;
An explanation of the adsorption of gas onto solids
An explanation of the adsorption of dissolved solutes or solvent onto solids
Cohesive force that can exists between solid particles and their potential effect on the
flow of powders

ADSORPTION OF GAS

The type of adsorption isotherms for gas

Explain the Freundlich isotherm in detail, including the equation
Explain the Langmuir isotherm in detail, including the equation and the assumptions.
Mention the applicability for certain assumptions for chemisorption
Explain the Branauer, Emmet, Teller (BET) isotherm in detail, including equation and
different types relating to the adsorption behavior and conditions. Mention the types
which the equation is applicable to.
Additional reading on the conclusions, conception and deviations from the three
isotherms.

Application of adsorption isotherm for gas

Discuss the applicability of these isotherm in determining or predicting certain

physicochemical characteristics. For examples;
- The solid-gas and gas-gas affinity, based on the isotherm curves. Explain that the
affinity is proportional to the steepness of the curves and give examples to
illustrate this. Compare by means of diagrams, the solid-gas affinity for the
different types of BET isotherms.
- Physical or chemical interactions can be distinguished by performing desorption
studies. Describe the involvement of physical and/or chemical interactions for
certain isotherms. Elaborate on the presence or absence of gas-gas interactions
(cohesive forces) and/or solid-gas affinity (adhesive forces) in the different
isotherms.

- Solid characteristics such as;

porosity. Discuss the presence or absence of pores and the degree of porosity based on
studies with gas.
 adsorption capacity
 effective or specific surface area. Define the relevant equations
 average particle diameter
- Choice of gas adsorption materials. Explain the factors that constitute good
adsorption materials. Examples of the materials (activated charcoal, silica gel,
calcium cloride, etc) and their behaviour.
- Other uses include;
• prediction of rates for various processes. Give examples.
• selection of appropriate product packaging. Elaborate.

Factor affecting gas adsorption

Describe and explain the factors that affect gas adsorption, including:
 Affinity
  Types of bonding
 Solid characteristic
 Gas pressure
 Temperature

An example showing the effect of temperature on physical adsorption:

Mass of NH3 ↑ T, ↓Q.

-23oC
adsorbed by 1g or No interaction
charcoal between NH3
0oC
molecules
80oC

100oC
P

Another example:

30oC ↑ temperature, ↓Q, ↓Qk

Amount of water Isotherm altered.
vapor adsorbed by Interaction between the
charcoal 100oC vapor molecules

Adsorption from solution

The types of adsorption isotherm for dissolved solute
 Describe and explain the adsorption of dissolved solutes by solids, including its
isotherms and outline a simple study to determine the extent of adsorption
(involving two sets of solution, one acting as control and the other containing
various quantities of solids) Describe the construction of the isotherm curves
based on the results of the study (y axis: amount adsorbed/weight of solid, x axis:
concentration of solution at equilibrium)
 Outline the different types of adsorption isotherm for dissolved solutes onto solids
(constant, High affinity, Langmuir and slow) and the factors that affect them
  Give in detail and discuss the characteristic of the different isotherms. Include the
physicochemical interactions and the affinity between the components, and the
conditions that affect them.

Application of adsorption isotherm for dissolved solute

Describe and explain the information from the adsorption of dissolved solutes onto
solids, including:
• Affinity of dissolved solutes to solids
• Elucidation of the characteristics of the solids (for examples, porosity,
surface area, particle diameter, etc)
• Determination of an appropriate solids act as an adsorber (for toxins, drug
overdose, bile secretions, water, etc.)

and drug carrier (affinity of drug to the adsorbing solid can be reduced at the target site or
at certain pH range in order to release the drug at a controlled rate.
• Compatibility of highly soluble drugs with insoluble or less soluble drugs
during coadministration (possible reduction in adsorption and
bioavailability due to the adsorption of the highly soluble drug by the
insoluble drug). For example, the adsorption of dissolved lincomycin onto
kaolin
Concentration of
Lincomycin in the
blood

(1)
Minimum
(2) therapeutic
concentration
(3)

time
Treatment
(1) lincomycin on its own
(2) Lincomycin given 2 hours after kaopectate
(3) Lincomycin and kaopectate given together

Factors affecting adsorption from solution

Discuss the factors that affect the adsorption of dissolved solutes, including
Concentration of dissolved solutes
Temperature (explain the influence on physical adsorption and the rate of chemical
reaction)
Surface area and average particle diameter (in terms of the influence on Q) porosity (in
terms of the influence on Qk and the area between the adsorption and desorption curves)
Affinity between dissolved solutes and solids, which in turn is affected by:

Solubility of solutes.
Discuss in terms of bonding between dissolved solutes and its solvent being difficult to
break; adsorption is inversely proportional to solubility
b. Ionization of dissolved solutes
An increase in the degree of ionization usually leads to a decrease in adsorption and
vice-versa. Mention that the ionization process can effected by pH.
For example:
% benzocaine
adsorbed by
nylon (low
polarity)

% ionized benzocaine % non-ionized benzocaine

Can be influenced by pH

In addition, mention the condition that leads to maximum adsoption for amphoteric
substances
c. Polarity or changes on the solid surfaces
For example:
At a pH whereby the solubility of atropine is lower than hyoscine, theory dictates that the
adsorption of atropine is higher than hyoscine. On the other hand, at the same pH, all of
the hyoscine exists in non-ionized form whilst 50% atropine is in ionized form.
Therefore, theory dictates that the adsorption of hyoscine is higher than atropine
Adsorption studies with magnesium trisilicate revealed that the adsorption of atropnie is
higher than hyoscine, suggesting that the low solubility of atropine is more significant
than the low degree of ionization for hyoscine. However, the high atropine adsorption
was actually due to its positively charged ions being easily adsorpbed onto the negatively
charged surface of magnesium trisilicate.

An additional example;
 Polarity and charge strength
Mg trisilicate> MgO>CaCO3
Therefore the affinity of the
% digoxin
antacids toward the positively
adsorbed by Mg tris.
charged digoxin also follows in
the antacids
that order

MgO

CaCO3

Concentration of drug

Other application of adsorption from solution studies

Outline other uses of dissolved solutes adsorption studies such as chromatography,
purification process, packaging, blood dialysis and the determination of absorption and
reaction sites.
For examples,
IV solutions can be stored in plastic begs or infused by using administration sets made
from polyvinyl chloride (PVC). Up to 50% nitroglycerin can be lost when the drug
solution is stored in PVC infusion bags for 7 days at room temperature. The drug could
be recovered from the inner surface of the bags using a more non-polar solvents,
methanol. Hence, the initial loss was attributed to adsorption rather than chemical
degradation.

The tendency for adsorption will depend on the relative affinity of the drug for the
hydrophobic PVC and the hydrophilic aqueous infusion medium. Other drugs that could
be adsorbed onto PVC are diazepam, insulin and isosorbide dinitrate.

• Recap briefly the relationships between free energy, surface area and surface
tension

W=γ.ΔA
W = work (Nm)
γ = Surface tension (nm-1)
Δ A (m2)

Surface energy is minimum if surface tension is less, surface tension is less by reduce the
surface area.

• Describe the difference in free energy between the surface of a solid and the bulk
solid
Existence of free energy at surface of solid
- At surface, attraction more toward bulk. à γ high
- At bulk, attraction is balanced in all directions. à γ low
Atom or molecules are close to each other and in compact arrangement. Cannot move
freely like in liquids. γ reduction through surface contraction is not effective or
significant.

Describe the process that occurs at the interfaces of solid-air, solid-liquid and solid-solid,
including;
An explanation of the adsorption of gas onto solids
An explanation of the adsorption of dissolved solutes or solvent onto solids
Cohesive force that can exists between solid particles and their potential effect on the
flow of powders

i) Between surface of air and solid

Gas atoms or molecules, when very near or collide with surface of solid, can form ◊ gas
adsorption.
The extent of gas adsorption onto solids depend on:
The chemical properties of adsorbent and gas
Total surface area of adsorbent
Temperature and partial pressure of gas

Quartz
spring Gas, it will be adsorbed by powder

Sample of
granules or
powder

ii) Between surface of liquid and solid

Solvent molecules, when touch the surface of solid, can form bonds ◊ solute or solvent
adsorption
iii) Between solid surfaces (cohesion)
Solid powder or particles, when very near to each other or touch, can form cohesive
attraction among particles and reduce a little of the free energy.
◊ Practically cohesion between particles can reduce powder flow from the container
through the punch of rotation tabletting machine
The type of adsorption isotherms for gas

If physical adsorption occur ◊ weak ◊ can be reversible (desorption). Desorption – occur

by increasing the temperature or reduce gas pressure

If chemical adsorption/chemisorption occur ◊ stronger ◊ irreversible

Chemical
interaction II III IV V
x x x x
m x
m m m m
Physical
interaction P
P P P

Explain the Freundlich isotherm in detail, including the equation

Freundlich Adsorption Isotherm

 x
Equation : = k P1/n
m
x
= k P1/n
x m
m

x
If P is increased m will be increased, no limit nor plateau

Freundlich equation:
log x = log k + 1/n log P y =c+mx
m

log x
m
Slope = 1/n

log k

log P
n and k are constants related to the rate of adsorption of a particular gas onto a particular
solid surface, and is affected by temperature

Explain the Langmuir isotherm in detail, including the equation and the assumptions.
Mention the applicability for certain assumptions for chemisorption

Langmuir Isotherm
x Q
- A limit exist
m

P Po

Assumes that:
i) short bonds are involved
ii) Only 1 layer of gas atoms/molecules adsorbed
iii) Adsorbed atoms/molecules remain at their positions.
iv) Rate of adsorption depends on the total number of vacant positions
v) Rate of desorption is related to the occupied positions.
i – iv ◊ suitable for chemical adsorption
v ◊ unsuitable for chemical adsorption
 Langmuir Equation P P 1
= +
x
Q aQ
m
P

x
m

slope = 1/Q

aQ

Po

Q = adsorption capacity
= amount of gas required to form monolayer for covering
the whole of solid surface

adsorption rate
a=
desorption rate

Q and a = constants
Explain the Branauer, Emmet, Teller (BET) isotherm in detail, including equation and
different types relating to the adsorption behavior and conditions. Mention the types
which the equation is applicable to.

BET Brunauer, Emmett & Teller Isotherms

Additional layers and condensation in the pores will occur when P approaches Po
(saturated vapor pressure)

Equation:
 P 1 h-1 P
= + x
x (Po-P) Qh Qh Po
m

P h-1
Slope Qh
(Po-P) =

1 Suitable
Qh for types
II and IV
P/Po

h = constant related to Ea (heat of adsorption) and Ec (heat of condensation)

h = e–(Ea-Ec)/RT

Additional reading on the conclusions, conception and deviations from the three
isotherms.
Application of adsorption isotherm for gas

Discuss the applicability of these isotherm in determining or predicting certain

physicochemical characteristics. For examples;
The solid-gas and gas-gas affinity, based on the isotherm curves. Explain that the affinity
is proportional to the steepness of the curves and give examples to illustrate this.
Compare by means of diagrams, the solid-gas affinity for the different types of BET
isotherms.

Uses of adsorption studies

A) To determine or predict gas-solid and gas-gas affinities based on isotherm curves

x
m
B
Gas A with solids B,C and D
C
D

Affinity is correlated with the steepness of slope

a) Affinity of gas A with solid B > solid C > solid D
b) No gas-gas interaction.

c) Affinity of gas with solid for I, II and IV type > III, V type
 IV V
II
III
I

No gas-gas
interaction

1. Isotherms II, III, IV, V ◊ gas-gas interactions present

2. Isotherm II and IV ◊ gas-solid (cohesive) interaction > gas-gas (adhesive) affinity or
interaction

3. Isotherm III and V◊ gas-gas (cohesive) affinity > gas-solid (adhesive) affinity or
interaction
Additional layers and condensation in the pores will occur when P approaches Po
(saturated vapor pressure)

Equation:

P 1 h-1 P
= + x
x (Po-P) Qh Qh Po
m

P
(Po-P)
h-1
Slope Qh Suitable
= for types
1 II and IV
Qh P/Po
h = constant related to Ea (heat of adsorption) and Ec (heat of condensation)
h = e–(Ea-Ec)/RT

B) Types of interaction
Physical Chemical (only form monolayer)

Isotherm I physical interaction or

chemical interaction Can be determine
through desorption
studies

x Chemical interaction
m Q due to strong attraction
(chemically interaction),
can not reverse as
Physical interaction
previously)
P

Isotherms II, III,IV and V ◊ involved physical interaction only or chemical interaction for
the first layer and physical interaction for successive layers
Can be determined through desorption studies
x x x x
m m m m

P P P P

II III IV V

C) Properties of the solid

i) Porosity
Isotherms I (physical or chemical)
- cannot establish whether porous or not. To determine, must study with gas that has
cohesive bonds and conducted at low temperature (physical adsorption can occur easily
and additional layers can be formed easily)
- if obtain
Isotherms II or III ◊ non porous
Isotherms IV or V ◊ porous

Qk
x
m
Q

P
Degree of porosity correlated with Qk and area between adsorption and desorption curves
ii) Adsorption capacity, Q
Q ◊ amount of gas to form a monolayer. Can be determined from the graph of isotherm
(P vs x/m) or graph of Langmuir equation (P vs P/(x/m))
Q↑ ◊ adsorption capacity ↑

iii) Effective or specific surface area

a) If Q in mol/g:
Sw = Q N A
N = avogadro no

M
A = 3.464 4ρ√2N
( )

M = Molecular mass of gas

Ρ = density of gas
b) If Q in ml/g

Sw = QNA
Vm Vm = molar volume (22.4 l/mol)

iv) Mean particle diameter

D= 6
ρSw

ρ = density of solid

D) Selection of gas adsorbent materials

Good adsorbent (based on information A ◊ C)
- Sw > 1 m2/g (d decrease , Q increase)
- Porous (Qk increase, area between curves increase)

- Affinity toward gas high (value of a increase)

- Reversible (physical adsorption) so that solid can be re-used
So a suitable solid is one that produces isotherm IV when interacting with gas
Examples of gas adsorbents
Activated charcoal ◊ in gas masks & packets put together with solid preparations

Hygroscopic i.e. remains solid

even though adsorbed a lot of
Silica gel, water vapor (40% weight of
alumina adsorbent)

CaCl2, Deliquescent i.e. becomes liquid

Phosphorus if lots of water vapor is adsorbed
pentoxide It must be kept separate from
preparations

E) Other Uses
a) To predict the rates of:
i) Dissolution of soluble drugs
ii) Absorption & bioavailability of drugs
iii) Reaction
iv) Cohesion between powder particles
Physical or chemical process ~ Sw
~ 1/d
b) Selection of product packaging
Product such as tablets, granules, powder, capsules, if found to adsorb O2, CO2, water
vapor, can undergo chemical changes, oxidation & reduction, and physical changes to
affect dissolution, cohesiveness etc.
à Result in changes in: reducing the potency, powder flow
 à Must be stored in containers with have been proven to be impermeable and put
together with packets of suitable adsorbent

Factors affecting gas adsorption

Affinity

1. Gas-solid ◊ high ◊in I, II, IV type

◊ low ◊ in III, V type
2. Gas-gas ◊ none ◊ I
◊ present ◊ II, III, IV, V
gas-gas affinity > gas–solid affinity

B. Type of bond
Strong à chemical adsorption
Weak à physical adsorption Determine with desorption
studies

C. Properties of solid
i) Diameter ↓; Sw ↑, Q↑.
ii) Porosity ↑; Qk ↑, area between curves↑

D. Gas Pressure
P ↑ ◊ x/m ↑ until a certain limit ◊ Q or Qk
P ↓ ◊ x/m ↓ for physical adsorption
◊ x/m remain at Q for chemical adsorption
E. Temperature
T ↑à physical adsorption ↓
T ↓à physical adsorption ↑ x/m for chemical adsorption
constant, only rate changes
 Example of the effect of temperature on
physical adsorption:

Mass of NH3 -23oC ↑ T, ↓Q.

adsorbed by 1g No interaction
or charcoal 0oC between NH3
80oC molecules
100oC
P

Another example:
30oC ↑ temperature,
Amount of
↓Q, ↓Qk
water vapor
100oC Isotherm altered.
adsorbed by
Interaction exists
charcoal
between the
vapor molecules
P

Adsorption from solution

The types of adsorption isotherm for dissolved solute

Describe and explain the adsorption of dissolved solutes by solids, including its isotherms
and outline a simple study to determine the extent of adsorption (involving two sets of
solution, one acting as control and the other containing various quantities of solids)

Describe the construction of the isotherm curves based on the results of the study (y axis:
amount adsorbed/weight of solid, x axis: concentration of solution at equilibrium)

Adsorption of solute by solid

Solution

Solvent one or more solutes

Move freely through brownian motion and can collide/touch the surface of solids, and if
affinity exists, can form a band and adsorb physically or chemically.

Isotherms of solute adsorption onto solids

Graph relates the concentration of solution at equilibrium with the amount of solute
adsorbed onto the surface of one unit mass of solid, at specified temperature.

Studies

a) Prepare solutions of various concentrations (from the lowest to near saturation)

b) Determine the UV absorption (or other methods) to obtain a standard curve.
c) Each concentration is put into 2 different container; one set without solid and
another set with solid of certain mass.

Set 1

Set 2
d) Allow equilibrium to be reached ◊ concentration does not change after adsorption by
container (set 1) and container and solid (set 2)
e) i) determine the concentration in set 1 ◊ initial concentration, and calculate initial
amount in solution
ii) determine the concentration in set 2 ◊ concentration after adsorption, and calculate
amount left in solution

Amount adsorbed = initial amount – amount left

Draw graph to determine isotherm

Amount
adsorbed/
mass of
solid

Concentration at equilibrium
(concentration of set 2)
 Types of isotherms
C (constant)
Amount H
adsorbed/
mass of H (High affinity)
solid
L (Langmuir)

S (slow)

Equilibrium concentration (C)

Types of isotherms is affected by:

Affected by
Affinity (high, low)
competition
Interaction (chemical, physical)
solubility
Ionization ∆ pH
Surface charge
Physical properties of solid (d, Sw, porosity)

Determination of interaction and affinity of solutes

a) Isotherm L
i) affinity of solute-solid > solute-solvent and solute-solute
ii) Forms monolayer before additional layers
iii) No competition
iv) Chemical or physical interaction (need desorption studies)
 b) Isotherm C
Adsorption occur easily because:
i) Affinity of solute-solid>solute-solvent and solute-solute
ii) Surface area or place for adsorption to occur very big ◊difficult to fill
rate of adsorption constant at the major part of the curve ◊e.g. fibrous materials
iii) Presence of competition does not greatly affect except steepness of slope and
Q may be a little lower

c) Isotherm H
Adsorption is very easy
i) Affinity of solute-solid >>> solute-solvent and solute-solute
At low initial concentrations, all of the solutes is adsorbed, none left in the
solution (equilibrium concentration O ◊ amount adsorbed high)
Solute prefer to be at interface than solution ◊
Surfactant (surface active agent)
Changes when : - affinity reduces
- competition present
- chemical, solubility changes

d) Isotherm S
Adsorption low or difficult at low Ceq due to:
i) Affinity between solute-solid< solute-solvent << solute-solute, when adsorption
has occurred, additional layers can form easily even though the monolayer has not
formed or
ii) Chemical interaction between solute-solid, but places limited. Physical interaction
of solute with those already adsorbed occurs easily or
iii) Competition from other types of solute present
Places for chemical or physical bonds to form limited (party filled by other
solutes already). Physical interaction of solutes with those already adsorbed occurs easily

Changes when:
- Affinity changes
- Type of interaction changes
- Competition reduces

Uses of adsorption studies

A) Affinity of solute-solid
Can be predicted from the initial gradient of the slope of the curve
 B. To determine characteristics of adsorbent
Q ◊ to determine Sw and d
Qk ◊ total number of pores. Porosity or volume ≈ area between adsorption and
desorption curves
Isotherm C ◊ total places or area for adsorption very high, unlimited

C. To determine a suitable adsorbent

1. To adsorb;
a. Toxin – diarrhoea eg. Kaolin
b. Excess active substance – poisoning eg charcoal

. Bile secretions – to reduce cholesterol eg cholestyramine

d. Fats – eg chitosan
e. Water

diarrhoea ◊ to solidify eg. Polycarbofil

Constipation ◊ to soften eg methylcellulose

ii) To carry active substances:

- Adsorbent should be able to adsorb active substance in great quantities during
preparation
- Need to release the active substance at a particular location or pH. Active
substance adsorption affinity at the site of absorption should reduce so that the
active substance can be released at the required rate.

θ = theta
Φ = phi
α = alpha
Γ = gamma
π = pi
γ = gamma
ρ = rho
η = eta