You are on page 1of 91

CHAPTER-3

Interfacial Phenomena
Dinberu B.(Bpharm, Msc in Pharmacology)

1 Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Objectives
2

After this lesson the students are expected to:

 Understand surface and interfacial tensions, adsorption


at liquid and solid interfaces

 Differentiate gas/liquid and liquid/liquid solutions and


solubility of different types of solids in liquids

 Understand the distribution law, and its applications

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface and Interfacial Phenomenon
3

 When two phases are in contact with each other, the


boundary b/n them is referred to as interface.

 If one of the two phases is a gas or vapor, the term


surface is generally used instead of interface.

 Interface is the boundary of separation of two phases.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Types of interfaces
4

 Different types of interfaces are encountered, depending on


whether the two adjacent phases are solid, liquid or gas.
 Surface
 Solid surfaces
◼ Solid-gas interface
 Liquid surface
◼ Liquid-gas interface

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Types of interfaces…
5

 Interface

 Solid-liquid interface

 Solid-solid interface

 liquid-liquid interface

 Can we say gas-gas interface?

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Types of interfaces…
6

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Liquid interfaces
7

➢ When we have two phases immiscible with each other, the


boundary b/n two phases is known as an interface.

➢ The properties of the molecules forming the interface are


often sufficiently d/t from those in the bulk of each phase that
they are referred to as forming an interfacial phase.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface & interfacial tensions
8

Surface tension

 The molecules forming the interface behave differently from those in


the bulk of each phase.

 Forces of attraction generally exist b/n molecules in liquids and in


solids (also in gases though weak).

 Interfacial tension is interfacial region/boundary/interface b/n two


immiscible liquids or liquid-solid.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface & interfacial…
9

 Molecules in the bulk of the liquid are surrounded by other


molecules for which they have equal attraction.

 These forces tend to cancel each other and the net attraction
experienced by any point in the bulk will be zero.

 Molecules at the surface however do not have their


attraction forces properly balanced.

 They experience an inward force of attraction towards the


bulk of the liquid. Dinberu B(B. pharm, Msc in Pharmacology)
Sunday, February 12, 2023
Surface & interfacial…
10

 Interaction b/n gas molecules and b/n gas and liquid


are negligible compared to a much stronger interaction
b/n liquid molecules.

 The surface of a liquid therefore gets contracted and


molecules at the interface are pulled together.

 The force which has to be applied to counterbalance


exactly this inward pull is known as the surface tension
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Surface & interfacial…
11

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface & interfacial…
12

Interfacial tension
 Some tension is also present at the interfaces between

two condensed matters.


Why?
 Interaction within molecules of a liquid will differ from

interaction of molecules of two liquids.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface & interfacial…
13

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface & interfacial…
14

Substance Surface tension (mN/m) Interfacial tension (against


water) (mN/m)

Mercury 476 428


Water 72.8 -
Glycerol 63 -
Benzene 29 35
Heptane 19.7 51.2
Ethyl ether 17 11
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Measurement of surface and interfacial tension
15

 Methods available for the measurement of surface and interfacial


tension.

 Wilhelmy plate methods

 Ring method (du Nuoy tensiometer)

 Drop weight and drop volume methods

 Capillary rise method

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Wilhelmy plate methods
16

 The apparatus consists of a thin mica, glass or platinum plate


attached to a suitable balance

 When used as a detachment method, the plate is immersed in the


liquid, and the liquid container is gradually lowered.

 Where WL is the reading on the balance prior to detachment, W


is the weight of the plate in air and L and T are the length and
the thickness of the plate, respectively
 requires the contact angle that the liquid makes with the plate to
be zero
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
17

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Ring method
18

 Measures the force required to detach a platinum ring from a


surface or an interface

 where F is the detachment force and R1 and R2 are the inner


and outer radii of the ring
 Again, a zero contact angle of the liquid on the ring must be
assured or the equation will not hold
 This can be achieved by careful cleaning and flaming of the
platinum loop, or by the use of a silicone-treated ring for oils

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


19

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Drop weight and drop volume methods
20

 If the volume or weight of a drop as it is detached from a tip of


known radius is determined, the surface or interfacial tension can be
calculated.

 where m is the mass of the drop, V is the volume of the drop, p is the
density of the liquid, r is the radius of the tip, g is the acceleration
due to gravity and ɸ is a correction factor (v/r3)
 At the point of break of the drop, up ward force equal to down
ward force(mg=2πrY)

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Capillary rise method
21

 Used a little in pharmaceutical research


 It is considered to be the most accurate
 If a capillary tube is placed in a liquid, provided the angle of
contact that the liquid makes with the capillary tube is less than
90°, the liquid will rise in the tube to a certain height.

 Where pL - pV is the density d/ce b/n the liquid and its vapor, rt is
the radius of the capillary tube
 g is the acceleration due to gravity and h is the height of the liquid
in the capillary tube.
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Factors affecting surface tension
22
1. The surface tension decrease with increase temperature.

Temperature increase-> KE of liquid also increase, intermolecular force


decrease, decrease inward force, decrease surface tension.

2. The surface energy may altered by the addition of solutes

 that migrate to the surface and modify the molecular forces there.

 Surface energy: quantifies the disruption of the intermolecular bonds that


occurs when a surface is created. It is also called(surface free energy or
interfacial free energy)-work per unit area done by the force to create SA.
 The contracted surface thus represents a minimum free energy state and any
attempt to expand the surface must involve an increase in the free energy

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Factors affecting surface tension…
23

3. Molecules at the surface of liquid substance do not experience


the same force.
4. Hence the surface layer contract.
 The contraction of the surface is spontaneous; that is, it is
accompanied by a decrease in free energy.
-b/c there is a decrease in surface area(SA)
-Cohesive force b/n molecule causes the surface of a liquid to
contract to the smallest possible SA.
SA of liquid: the amount of liquid that exposed to the air,
touching the air.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Factors affecting surface tension…
24

 If one increases the surface (i.e., brings molecules from


the bulk of the phase to the surface), work (W) should
be done against the forces in the surface.

 The surface free energy is a measure of this work.


 It is the minimum amount of work required to bring the
molecules to the surface from the interior to expand the
surface by unit area. W is the work done
∆A = surface area
y = Interfacial tension
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Spreading
25

 If a small quantity of an immiscible liquid is placed on the surface of


another liquid, it will either spread as a film on the surface of the
other liquid or remain as a drop or lens.

 Each of the two applies generally depends on the achievement of a


state of minimum free energy.

 The ability of one liquid to spread over another can be assessed in


terms of spreading coefficient.
 Its value should be either positive or zero for spreading to occur
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Spreading…
26

Spreading coefficient((Wa – Wc)


 In general spreading of a liquid on the surface of another occurs
when the work of adhesion b/n the two liquids exceeds the work of
cohesion b/n the molecules of each liquid.
◼ Adhesional forces are forces which act b/n molecules of d/t
phases while cohesional forces are those which act b/n molecules
of the same phase.
◼ Cohesional forces tend to keep the phase separated while
Adhesional forces tend to increase the affinity of two phases.
◼ If Adhesional forces are strong, miscibility takes place.
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Spreading…
27

 The work of cohesion (Wc) may be considered as the surface free


energy increase produced by separating a column of pure liquid
into two halves.

 The free energy increase on increasing the surface area is given by:

WC =  L A +  L A WC =  L (A + A)

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading…
28

1 cm2 L L

L
L L

If the column of liquid has a cross sectional area of 1 cm2, the


equation becomes: based on the formula; W =  (A + A)
C L

WC =  L (1 + 1) WC = 2 L

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading…
29

 The work of adhesion (Wa) may be considered as the


free energy increase produced by separating a column
of two immiscible liquids at the interface into two sections.

1cm2
L
L L
LS

S S
S
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Spreading…
30

❑ When the surfaces of liquids L and S are separated from each


other, they have their own surface tensions, L and S.
 When the two surfaces come into contact with each other to form an
interface, an attractive force between molecules of L and S
appears.

 The work of adhesion is given by:

Wa =  L A +  S A −  LS A

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading….
31

 This attractive force partially compensates for the excess energy of


the molecules present at the surface of L and S and consequently
reduces the surface tension of two liquids.

 Assume the column of the liquid has a cross sectional area of 1 cm2,
then the equation becomes:

Wa =  L +  S −  LS

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading…
32

 The spreading coefficient (S) is the d/ce b/n the work of adhesion
and the work of cohesion (Wa – Wc).

 This implies that if the work of adhesion is more than the work of
cohesion, spreading will occur.

Wa − Wc =  L +  S −  LS − 2 L S =  S − ( LS +  L )
 Where,
 S refers to the surface tension of the sublayer liquid

 L refers to the surface tension of the spreading liquid

 LS refers to the interfacial tension between the two layers.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading…
33

 Spreading occurs when the surface tension of the sublayer is


greater than the sum of the surface tension of the spreading liquid
and the interfacial tension b/n the sublayer and the spreading
liquid. S =  S − ( LS +  L )
 If S is negative, i.e., when L + LS is larger than S, the spreading
liquid forms a globule or a floating lens and spreading will not
take place.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Spreading…
34

Liquid Spreading Coefficients (S) (dynes/cm)


Benzene 8.8
Hexane 3.4
Octane 0.2
Toluene 6.8
Ethanol 50.4
Acetone 42.4
Oleic acid 24.6
Chloroform 13.0
Hexadecane -9.3
Liquid paraffin -13.4
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Pharmaceutical applications interfaces
35

❑ The preparation of emulsions and suspensions, involves interactions


at the liquid/liquid and liquid/solid interfaces, respectively.

❑ the selection of a granulating agent(alcohol, acacia, tragacanth) to


form agglomerates, based on the measurement of spreading
coefficients and other surface properties,

❑ Similarly, film coating requires the spread of liquid over a tablet


surface.
❑ The successful dissolution of a tablet or capsule necessitates penetration of the
liquid into the pores of Dinberu
the dosage form
B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Pharmaceutical applications spereding
coefficent
36

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Applications of spreading coefficient in pharmacy
37

➢ Surfactants added to topical products to improve spreading:

➢ For a lotion with mineral oil base to spread freely and evenly on
the skin, its polarity and
➢ hence its spreading coefficient should be increased by the addition of
the proper SAA(wetting and dispersing agents, emulsifiers, lubricant)

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Quiz 1.
38

 Which one is example of solid surface?


A. solid-solid interface B. solid-liquid interface C.
solid-gas interface
❑ Which one is example of interface?
A. gas-gas interface B. liquid-gas interface C. liquid-
liquid interface
❑ Which one of the following method of measuring
surface tension relatively the most accurate?
A. Wilhelmy plate methods B. Ring method C. Drop
weight methods D. Capillary rise method

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption at liquid interfaces
39

Adsorption at Liquid Surfaces

 Certain solute molecules and ions, when dispersed in a liquid


get partitioned in favor of the surface or the interface and
this phenomenon is termed positive adsorption.

 Some other solute molecules or ions such as glucose and Nacl


are partitioned in favor of the bulk liquid and this termed as
negative adsorption.
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Adsorption at liquid interfaces…
40

 Solutes or molecules that are preferentially adsorbed at


the surface or interface of liquids reduce the surface or
interfacial tension termed as:
surface active agents or surfactants.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Surface-active agents
41

 Surface-active compounds are characterized by having two distinct


regions in their chemical structure; these are termed hydrophilic
‘water-liking’) and hydrophobic (‘water-hating’) regions.

 Amphiphiles

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants
42

 They are classified by their hydrophilic groups into:

➢ Anionic

➢ Cationic

➢ Non-ionic

➢ Amphoteric

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
43

Anionic surfactants
 These are surfactants in which the hydrophilic portion of the
molecule carries a negative charge.
 Not suitable for internal use
-unpleasant taste and
-irritant action on the intestinal mucosa.
Eg. Alkyl sulfate, Alkyl benzene sulfonate

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
44

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
45

Cationic surfactants

 These are surfactants in which the cation is the surface-active


component.

 Incompatible with anionic surfactants.


 eg. Quaternary ammonium compounds such as cetrimide, benzalkonium
chloride and benzethonium chloride.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
46

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
47

Amphoteric Surfactants

 Amphoteric surfactants can behave either as anionic or cationic


molecules, depending upon the pH.

 This surfactant can be in the anionic, cationic, or zwitter-ionic state


depending on the pH value of the solution it is in.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
48

Non-ionic Surfactants
 Have a water-soluble hydrophilic region.

 They are not electrolytes

 Have some non-dissociative hydrophilic group.

 Compatibility with both anionic and cationic surfactants.

 Resistance to pH change and effects of electrolytes.

 Lower irritancy as compared to other surfactants.

 The largest group of surface active agents that is useful

pharmaceutically.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Classification of Surfactants…
49

 Example
 Sorbitan monopalmitate (Spans)

 Polyethylene glycol sorbitan fatty acid esters (Tweens)

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Hydrophilic-Lipophilic Balance (HLB) system
HLB Systems
50

 Surfactants with more polar groups are predominantly hydrophilic


while those with more non-polar groups are predominantly lipophilic.

 The balance between these two groups can be given by means of

➢ Hydrophilic-Lipophilic Balance (HLB) system

❖ An arbitrary scale of values assigned to d/t surfactants based


on their nature.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


HLB Systems…
51

 In HLB system, each surfactant is assigned a number b/n 1 and 20


representing the relative proportions of lipophilic and hydrophilic
parts of the molecule.

 The higher the HLB value, the more hydrophilic the agent is.

 Depending on their HLB values, the surfactants have d/t uses.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


HLB Systems…
52

 Surfactants with HLB values of:

➢ b/n 3 and 6 are lipophilic and form w/o emulsions

➢ 8 to 18 indicate predominantly hydrophilic characteristics and


the formation of o/w emulsions.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


HLB Systems…
53

HLB value Agent

1-3 anti-foaming agents(simethicone)

3-8 w/o emulsifying agents

8-16 o/w emulsifying agents

16-19 solubilizing agents

7-9 wetting and spreading agent


Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
HLB Systems…
54

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Determination of HLB value of surfactants
55

 There are several empirical expressions to calculate the HLB values


based on the chemical structures present.

 The HLB of a number of polyhydric alcohols and fatty acid esters


such as glyceryl monostearate, can be calculated by using the
formula: HLB = 20(1 - S/A)
where
S is the saponification number of the ester
A is the acid number of the fatty acid.

 S no: indicate how much KOH is needed to saponify 1g of fat



Dinberu
Acid no: is a measure of the B(B. pharm,of
amount Msccarboxylic
in Pharmacology)
acidSunday,
groupFebruary 12, 2023 copd
in a chemical
Determination of HLB…
56

 But the saponification number for many substances like bees-wax


and wool-fat derivatives cannot be easily estimated.

 In such cases, the following relation is used:

HLB = (E + P)/5
 where E is the percent by weight of oxythelene chains and P is the
percent by weight of polyhydric alcohol groups in the molecules.

 Obviously, when the molecule consist only of oxyethylene groups,


equation becomes: HLB = E/5
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Determination of HLB…
57

Example
 A typical nonionic emulsifier (e.g. Laureth-4) contains an ethylene
oxide groups or polyhydric alcohol hydrophilic portions with a fatty
alcohol hydrophobic portion.
➢ Molecular weight of ethoxylate portion = 176
➢ Molecular weight of lauryl alcohol = 186

 Calculate the HLB value of the nonionic surfactant?


➢ Wt. % Hydrophile = (176/(176+186)) x 100 = 48.6%

➢ HLB = 48.6/5 = 9.7


Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Determination of HLB…
58

 It is not easy to match the required HLB value of the oil or the oil
mixture with that of a single surfactant to form the most stable
emulsion.

 The appropriate combination of surfactants (usually a binary


system) should be chosen. => most stable emulsion

 The HLB value of the binary mixture of surfactants A (HLBA) and B


(HLBB ) is calculated by:
Where fA is the weight fraction
of surfactant A in the mixture.
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Determination of HLB…
59

Example
 If a mixture of 20% paraffin wax (HLB =10) and 80% aromatic mineral
oil (HLB = 13) is to be emulsified then, how much will be the HLB number
of the mixed emulsifying agent? Ans: 12.4

 Where fA is the weight fraction of surfactant A in the mixture.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application of surfactants
60

A. As solubilising agents
 As solubilising agent for a number of poorly soluble drugs such as oil soluble
vitamins, volatile oils, phenobarbitone, sulphonamide, etc.

 Oil-soluble vitamins such as Vitamin A

- unpleasant to take in the form of fish liver oil


◼ Are easily palatable when administered in the form of oil in water
emulsions(O/W) or as solubilized in water.
 Preparation of aqueous injections of the water-insoluble vitamins A, D, E, K.

 Solubilization of steroids in water for ophthalmic use.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application…
61

B. As wetting agents
 Hydrophobic powders tend to aggregate and agglomerate when added to water.

 Dispersions containing such hydrophobic powders are often difficult to prepare


since the powders form large floccules or float on the surface.

 This problem is generally overcome by the use of SAA which get


adsorbed at the solid/liquid interface and

 increase the affinity of the hydrophobic powder for water while


reducing the attractive forces b/n particles of the solid.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application…
62

 Wetting means the contact angle b/n a liquid and a solid is zero or
close to zero so that the liquid spreads easily over the solid.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application…
63

 Contact angles characterize how easily liquids spread on a given


solid surface.
 Which is defined as the angle formed b/n the tangent drawn from
the drop at the three-phase interface and the solid surface over
which it spreads.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application…
64

 If the contact angle b/n a solid and a liquid is 0°, signifying


complete wetting,

 If it approach 180°, at which wetting is insignificant.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical Application…
65

C. As emulsifying agents
 These act by reducing the interfacial tension b/n the oil phase
and water phase by forming a stable interfacial film b/n the
two.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption at solid interfaces
66

 If a solid comes into contact with a gas or a liquid, there is an


accumulation of the gas or the liquid at the interface rather than in
the bulk of the solid.
 The term adsorption is used to describe this process of accumulation
at an interface.
➢ takes place on surface of solids having high surface free energy.

➢ Adsorption takes place to reduce this free energy.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption at solid interfaces…
67

 There are two main types of adsorption:

➢ Physical or van der Waals' adsorption, and


➢ Chemical or chemosorption
 In physical adsorption the molecules are held on the surface by van
der Waals' forces which are very weak.
➢ Heat of adsorption = about 20kJ/mol
 It is rapid and easily reversed either
 by raising the temperature or lowering the pressure.
 Multilayer adsorption is possible
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
68

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption at solid interfaces…
69

 In chemosorption the molecules of the adsorbate are held by


chemical bonds.

 It is characterized by higher heat of adsorption (about 80 kJ per


mole of adsorbate).

 It is rarely reversible.

 The thickness of the adsorbed layer is generally one molecule.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption at solid interfaces…
70

Comparison between physisorption and chemisorption


S. No. Physical adsorption Chemical adsorption
1 Caused by intermolecular van der Caused by chemical bond formation
Waals' forces
2 It is not specific It is highly specific
3 It is reversible It is irreversible
4 Heat of adsorption is low (20-40 kJ/mol) High heat of adsorption (80-240 kJ/mol)
5 Low temperature is favourable Increases with high temperature
6 Results multilayer adsorption Results unimolecular layer
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Adsorption at solid interfaces…
71

Solid/vapour systems
 Although adsorption in solid/liquid systems is of more interesting
pharmaceutically
 the interpretation of results is often achieved using equations developed for
solid/vapour systems

➢ If a gas or vapour is brought into contact with a solid, some of it will


become attached to the surface.
➢ This reduces the imbalance of attractive forces and hence the
surface free energy
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Adsorption isotherms
72

 When a gas comes in contact with a solid surface,


➢ molecules of the gas get adsorbed to the surface in quantities
that are a function of their partial pressure in the bulk
 The amount of gas adsorbed is often plotted against the equilibrium
pressure of the gas at constant temperature
 Such a plot is referred to as adsorption isotherm (isotherm refers to a plot
at constant temperature)

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Type I Isotherms
73

➢ It exhibits a rapid rise in adsorption up to a limiting value.


➢ referred to as Langmuir-type isotherms
➢ are due to the adsorption being restricted to a monolayer
➢ At low pressure the amount of gas adsorbed is proportional to the
pressure and at higher pressures the adsorption becomes less
➢ levels off to a constant value indicating that all the available sites have
been filled up

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Type II isotherms
74

➢ It represent multilayer physical adsorption on non-porous materials

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Types III and V isotherms
75

➢ They occur when the adsorption in the first layer is weak.


➢ They are rare.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Type IV isotherm
76

➢ It is considered to be due to condensation of vapour in fine


capillaries within a porous solid.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Isotherm equations
77

 Many equations have been suggested to explain the


relationship b/n the amount of adsorption and the
pressure of gas.
 Among the most frequently used isotherm equations:
➢ Langmuir adsorption isotherm

➢ Freundlich

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption isotherms…
78

Langmuir adsorption isotherm


 assumes that only monolayer coverage is possible

 it is only applicable to type I isotherms.

 the amount of gas or vapour adsorbed, x, by a given mass, m, of the


adsorbent at constant temperature.
 equilibrium pressures p, (the pressure attained after adsorption has taken
place) to yield an adsorption isotherm
 a is constant
 b : amount of gas required to produce a monolayer over the whole surface of
the absorbent
 plotting pmlx against p give a straight line with a slope l/b and intercept 1/ab

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption isotherms…
79

1. Freundlich Adsorption isotherm


 It is given by:

 X/Y= amount of gas adsorbed

 Where,

➢ X is the mass of gas adsorbed

➢ m is the mass of adsorbent

➢ K and n are constants that depends on temperature and nature


of adsorbent and adsorbate
➢ P is the equilibrium gas pressure
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
➢ Y is the mass of gas adsorbed per unit weight of adsorbent
Adsorption isotherms…
80

 A plot of x/m (or y) against p, the equilibrium pressure, yields a


curve as shown below

x/m 1
log y = log k + log p
n

Pressure

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Adsorption isotherms…
81

 Adsorption isotherm for a gas on a solid obtained by plotting log


x/m against log pressure.

The logarithmic form of Log x/m


Freundlich equation is:
A plot of log y against
log p yields a straight
line Log pressure
Slope = 1/n
Y intercept= log k
Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Solid/liquid systems
82

 Adsorption of a solute in solution on to a solid

 Such type of adsorption of solute molecules from its solution is more


complicated

➢ since there may be competition of the solute and the solvent


molecules for the solid/liquid interface.

 Thus adsorption on solids is a function of the relative adsorption of


the solute and the solvent.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Solid/liquid systems…
83

 However, at low concentration of solutions, the adsorption of solute


molecules onto solids is somewhat similar to that of gas adsorption
onto solids.

 Langmuir adsorption isotherm equation with slight modifications


can be used to describe the adsorption pattern.

 In this case the vapor pressure term is used for solid/gas


adsorption is replaced by solute concentration.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Factors affecting adsorption from solution
84

 Solute Concentration

 There is an increase in the amount of adsorption with an


increase in the concentration of solute at equilibrium until it
reaches a limiting value.

 Temperature

 Adsorption is generally exothermic, and hence an increase in


temperature leads to a decrease in adsorption.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Factors affecting adsorption…
85

 Surface area of the adsorbent


 reduction of the particle size of the adsorbent will result in an
increase in the surface area and hence an increase in the
adsorption
 Adsorbed impurities
 Adsorbed impurities such as gases or moisture on the surface of
solid adsorbent decreases the efficiency of adsorbents
 heating at high temperature (at 110oC for 1h) removes these
impurities to activate the adsorbent and efficiency is increased

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Factors affecting adsorption…
86

 pH of the medium
➢ Depending upon whether the ionized or unionized species are
more strongly adsorbed, the adsorption would increase or
decrease with a change in pH.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Pharmaceutical applications of adsorption
87

 Desiccants and Drying agents

➢ Traces of water from organic liquids can be removed by shaking


with an adsorbent such as alumina or silica gel.

➢ Silica gel contained in small packets are used to provide a dry


atmosphere inside the containers of pharmaceutical solid
products to protect them from high humidity which may
adversely affect the product.

➢ Are hygroscopic substance used to sustain dryness


Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023
Medical & pharmaceutical applications…
88

 Adsorption Chromatography
➢ This is a separation technique based upon the affinity of solutes
to the adsorbent molecules.
➢ solute with greater affinity for the adsorbent is strongly bound
➢ solute that has less affinity and which elutes first from the column

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Medical & pharmaceutical applications…
89

 Adsorption of poisons/toxins
➢ Activated charcoal: tablets or capsules or powder
✓ Digoxin, TCA, theophyline ,strong acid and base drugs

 Taste masking

 Haemoperfusion
➢ Carbon haemoperfusion is a method of treating cases of severe
drug overdoses.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


Medical & pharmaceutical applications…
90

 Drug formulation

➢ Adsorption of surfactants and polymers in the stabilization of


suspensions.

➢ Improvement of the dissolution rate of poorly water-soluble


drugs by adsorption of small amounts of surfactant on to the
drug surface.

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023


91

Thank you!!!

Dinberu B(B. pharm, Msc in Pharmacology) Sunday, February 12, 2023

You might also like