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UNIT-III
SURFACE & INTERFACIAL PHENOMENON

Points to be covered in this topic

1. LIQUID INTERFACE, SURFACE,INTERFACIAL
TENSION

2.SURFACE FREE ENERGY

3.MEASUREMENT OF SURFACE &

INTEREACIAL TENSION

4. SPREADING CO-EFFICIENT

5. ADSORPTION OF LIQUID INTERFACE

6.SURFACE ACTIVE AGENTS

>7.HLB SCALE

8.SOLUBILISATION

9.DETERGENCY

10. ADSORPTION OF SOLID INTERFACE

OINTRODUCTION SURFACE

Interface is the boundary that formed INTERRFACE

between phase ,say solid &liquid.
3 Surface is term used to denote interface
in which one of the phase in gas. 0 are two different phases
Surface is the term used to describe either a gas-solid or a gas-liquid
interface.
OLIQUID INTERFACE
Different types of interface can exist depending on whether the two
adjacent phases are in the solid, liquid, or gaseous state.
For convenience, these various combinations are divided into two groups
such as liquidinterfaces and solidinterfaces.
" Solid interfaces will deal with systems containing solid-gas and solid
liquid interfaces.
The association of aliquid phase with a gaseous or another liquid
phase.
OSURFACE & INTERFCIAL TENSION
&Surface tension Vapor phase

Surface tension is defined as tensile force

acting at the surface of liquid which is in +0+

contact with gas.
The net effect is that the molecules at the

surface of the liquid experience an

inwardforce toward the bulk.
Such a force pulls the molecules of the
interface together and, as a result,
contracts the surface, resulting in a Liqud phase

surface tension.
 The surface tension, has the units of dynes/cm in the CGS system and of
N/m in the SI system.
The term surface tension is reserved for liquid-vapor (Y), and solid
vapor (Y)tensions.
Cohesive forces:
The intermolecular attraction between the similar molecules is
called thecohesive force.
For example:- Molecules of water in bulk are surrounded the similar
types of molecules and the intermolecular forces between them are
the force attraction.

Adhesive forces:
The force between the unlike molecules is called the adhesive force.
" For example:- Molecules of water at the surface behave differently than
the molecules in the bulk.

Phase 2 (Oi)
Molecule in
bulk of liquid

Dissimilar molecules
at surface

Molecules In bulk
of liquld

Phase 1(Water)

Fig:- Adhesive &cohesive force

 Interfacial tension
" It is the force per unit length existing at the interface between two
immiscible liquid phase.
" If two liquids are completely miscible , no interfacial tension exist
between them.
" CGS = dynes/cm Cohesive force
Betneen like molecules
When phases exist together, Adhesive forces
the boundary between two of Beteenunlke
moleades
them is known as an
hetace
interface.
Cohesive forces
Interfacial tension for the 00 0 Betneen ike
force between
liquids(y), between
two

two
ooo4o molecues

Water
solids(Y.) and at a liquid Fig:- Formation of interface between oil &
solid interface (Y) water

Interfacial tensions are less than surface tensions because the adhesive
forces between two liquid phases forming an interface are greater than
when aliquid and a gas phase exist together.
Classification of interfaces
Phase Interfacial Types Examples of interfaces
tension
No interface
Gas-gas possible

Body of water exposed to

Gas-liquid Yv Liquid interface
atmosphere
Gas- solid Solid surface Table top
Ysv
Liquid- liquid Liquid-liquid Emulsion
interface

Liquid -solid Liquid-solid

YLS interface Suspension

Solid-solid
Solid-solid Yss Powder particles
interface
OSURFACE FREE ENERGY
To move a molecule from the inner layersto the surface,work needs to
be done against the force of surface tension.
Each molecule near the surface of liquid possesses a certain excess of
potential energy as compared to the molecules in the bulk of the
liquid.
The higher the surface of the liquid, the more molecules have this
excessive potential energy.
Surface of the liquid increase, energy of the liquid also increase.
Energy is proportional to the size of the free surface is called surface free
energy.
To evaluate the amount of work in increasing the surface area.
Equation may bewritten as yx 2L =f
Surface tension maintains the surface area of a liquid to a minimum
value.
Surface free energy is defined as the work required to increase the area
of a liquid by 1 square meter.
Surface free energy is equal to the surface tension.

The mass is added to extend the surface by a distance ds the work dw

[force x distance] can be written as
dW =fx d, =yx 2Lx ds
and ,since 2L xd, is equal to the increase in surface area dA produced
by extending the soap film
Stationary bar
dW= ydA
For a finite change Moyable ber

W=yAA
Fig :- Wire frame apparatus >Welght
used to demonstrate the
principle of surface tension
W= Work done, or surface free energy increase, expressed
in ergs,
y= Surface tension in dynes/cm
AA= Increase in area in cm.

OMEASUREMENT OF SUREACE & INTERFACIAL TENSION

Surface and interfacial tension is very important physio-chemical
property which affects the surface chemistry of the substances whether
solid, liquid or gas.
There are many methods for the measurement of surface and interfacial
tension

Methods for measurement of surface &interfacialtension

Sr.No. Name of method Measurement
1 Capillary rise method Surface tension

2
Drop formation method Surface tension
(stalagmometer)
3 Bubble pressure method Surface tension

4 Wilhelmy plate method Surface tension & interfacial tension

5 DuNouy ring method Surface tension & interfacial tension

1. Capillary rise method

Principle
When a capillary tube of radius 'r' is vertically inserted into a liquid, the
liquidrises to aheight 'h' and formsa concave meniscus.
This is because of the adhesive forces between liquid molecules and
glass are stronger than cohesive forces between liquid molecules.
 The liquid is said to wet the capillary wall, spreading over it, and rising in
the tube.

The rise in the tube continue until the upward movement is just balanced by
thedownward force of gravity due to the weight of the liquid.

2r k

For most
Liqusd
liquids 0 0

Fig A:- Measuring surface tension Fig B:- Force components and
by meansof the capillary contact angle at the meniscus
rise principle. of a liquid.

The upward vertical component of the

force resulting from surface tension on
the circumference isgiven by
a =ycos0
The total upward force around the inside
circumference ofthe tube is

2Try Cos 0
Where, 0= contact anglebetween surface
of liquid and the capilary wall. Fig:- Travelling microscope
2Tr = Inside circumference of the capillary
For water is insignificant as shown in Fig. (B).
Where,
Y
(Gamma)= Surface tension of liquid
r= Radius of capillary tube
h= Height of liquid rise in the capillary
p= Density of liquid
g= Acceleration due to gravity
Procedure:
i. Take appropriate size of capillary, clean and dry.
ii. Focus the travelling microscope to measure internal diameter of the

capillary tube.
iii. Take 50 ml of liquid in 100 ml of beaker.
iv. Fix the capillary in a stand and dip in it on the surface of the liquid in
beaker.

V. When liquid rises in the capillary, measure the height by travelling

microscope by focusing first at height meniscus, remove the beaker

and then focus at the tip of the capillary. Determine the density of
liquidby pycnometer.
2. Dron formation method (stalagmometer)
Principle
When liquid comes out of the capillary, it first forms a drop at the tip
of the capillary tube which gradually increase in size and finally
detaches from the tip.
The weight of drop equals to the total surface tension at the
circumference of the tube.

Hence,
Weight of drop = ST
m.g= 2ry
Where,
m= mass of drop
V.p.g=2Try
g= acceleration due to gravity
r=radius of the tip V.p-&
y= surface tension

The stalagmometer (Drop pipette) is the apparatus used for determination

of surface tension and one of the twomethods are used as given below.
i. Drop - Weight Method
i.Drop-number Method
i) Drop- Weight Method
This method is carried out by drop pipette or Stalagmometer which
consists of a glass tube with a bulb approximately at the middle of the tube.
There are two markings on the pipette marked as "A" and "B".
There is a capillary bore at the tip of the Stalagmometer.
" In a weighing bottle about 20 drops of liquid are received from
stalagmometer and weighed.
" Thus weight of one drop is found. Uppter stem
A
Fll ne
" Repeat the procedure for

second liquid (reference,

usually water) and weight of

B Capllary tube
Lowor stem with
one drop determined as before. Capllary bore

Using following equation one

can calculate the surface
Drop
tension of unknown liquid.
Fig:- Stalagmometer
 This method is carried out by drop pipette or stalagmometer which
consist of glass tube with a bulb approximately at the middle of the tube.
There are two markings on this pipette marked as "A" and "B".
There is a capillary bore at the tipof the stalagmometer.
Procedure:
1) Clean and dry Stalagmometer and fix vertically on the stand.
2) Suck given liquid up to the mark "A".
3) Allow liquid to drop slowBy from the tip,
4) Collect about 20 drops in aclean tared vessel and weigh.
5) Determine the weight of one drop by dividing weight of liquid by
number of drops.
6) Clean and dry Stalagmometer and fill it with second reference liquid
(say water) anddetermine the weight of one drop similarly as done
before from given liquid.

For test liquid - m,g= 2Tr (1)

For reference liquid m, g=2 Tr2 (2)

Dividing equation (1) by equation (2)

m,g 2r Y1
m2 8 2Tr Y2

Where

71 =surface tension of test liquid

2 = surface tension of reference (water) liquid

mj= weight of one drop of test liquid

m, =weight of one drop of reference liquid
ii. Drop-number Method
This method is carried out by drop pipette or Stalagmometer by sucking
the test liquid up is the mark 'A".

Keep the Stalagmometer vertically and allow the liquid fall in the form of
drop from mark 'A'to 'B', in aclean and dry beaker.
Count the number of drops.
Similarly count the number of drops of reference liquids (water) for the
same volume.

Suppose, n, and n, are the number of drops of test liquid and reference
liquid respectively produce volume Vfrom mark'A' to 'B.
Then volume of onedrop of test liquid = V/n,and the volume of one drop
of reference liquid=V/n,.
We know that

Mass of onedrop = Volume x density

Then, mass of onedrop of test liquid=n1x p (3)

Similary mass of one drop of reference liquid =n2 X P2 -(4)

Put the value of equation (3) in the equation (1), we get

nË
=21r1 (5)
" Put the value of equation (4) in the equation (2), we get
vp,g
n, 2rY2 (6)
Now divide equation (5) by equation (6) we get

vp,9 xn2mr'y,
X
vp,g 2 mrY,
n,
Pi= Density of test liquid
P,= Density of reference liquid
n,=Number of drops of test liquid
n,= Number of drops of reference liquid
Y,= Surface tension of test liquid
Y;= Surface tension of reference liquid (water)
3. Maximum Bubble pressure Method
" In this method the maximum pressure required to break a bubble at the
end of the capillary and at the moment of breaking it is determined.
Air pressure is applied slowly through a tube dipping in experimental
liquid. Abubble is formed and slowly growsand then breaks.
" The pressure at which the air bubble breaks is determined on
manometer and surface tension calculated using following formula.

p=maximum pressure
p= hdg +27 d=density of the liquid
Y= surface tension
h=depth ofliquid.
r=radius of capillary

Air pressure
-Capilary

Manometer Bubble

Fig:- Apparatus for Maximum bubble pressure method.

 4. WILHELMY PLATE METHOD
C
Wilhelmy plate method is used to measure equilibrium surface or
interfacial tension at air liquid or liquid-liquid interface.
Asimple apparatus consists of a glass, mica or platinum plate attached
with the torsion micro-balance.

The plate is oriented perpendicular to the interface and the force exerted
on the plate at interface between the two immiscible liquids or surface of
the liquid is measured using micro-balance.
When the vertically suspended plate touches the liquid surface or interface,
then a force F, which correlates with the surface tension or interfacial
tension y and with the contact angle 0, Thus, the force (F) exerted on the
plate is equal to the surface tension multiplied by the perimeter of the
plate 2(1+ d) and the contact angle cos is the length of plateand d is the
thickness of the plate.
The force exerted (F) is the difference in the balance reading prior and
after to detachment of plate, hence,
F (W,-W)
The plate is cleaned and dried.
After the plate is completely dried, it is attached to a balance with the
thin metal wire
B Fa Perimeter XST XContact angle
Beam
To torsion balance
A Platinum plate
Pertmetera 2 (1+d)

Rectangle plate
air

liquid
Fig:- Wilhelmy plate
Fig:- Wilhelmy plate method immersed in liquid
 Take the liquid in a beaker and the pale is immersed in the liquid now
the liquid containeror beaker is gradually lowered
The reading of the balance is noted immediately just prior to the
detachment of the plate and also the after detachment of the plate in the
air.

The surface tension y is calculated using Wilhelmy equation assuming

complete wetting of plate (0=0) , where 0 is the contact angle between
the liquid phase and the plate.
Since (0=0) hence, cos = 1.
Thus, the exerted force
F=2 (l+d). cos 0.y
(W -W) =2((+d) y
y=(WL -W)
Y2(+d)
W= Reading of the balance prior to the detachment of the plate
W= Reading of the balance after to the detachment of the plate
l= Width of plate
d=Thickness of plate

5. DuNouy ring method

The DuNouy tensiometer is widely used for measuring surface and
interfacial tensions.

The principle of the instrument depends on the fact that the force
necessary to detach aplatinum-iridium ring immersed at the surface
or interface is proportional to the surface or interfacial
One end of the torsion wire is fixed while the other attached to a knob
having a pointer which moveson a fixed scale.
 The force required to detach the ring in this manner is provided by
torsion wire and is recorded in dynes on a calibrated dial.

Dial

Adjusting knob

Ring

Sample tube

Fig:- DuNouy tensiometer

Rng Forca

|Surfece tension

Fig:- DuNouyring tensiometer

The representation of the tensiometer ring pulling a column of water above
the surface.
The surface tension can be computed from following formula
dial reading (dynes)
Y= 2xring ciecumference-xCorrection factor B
The correction factor is essential because certain variables must be
consider toavoid errors like radius of ring, radius of wire used to form
the ring and volume of the liquid raised out of the surface.

Procedure
The step-wise procedure to conduct the experiment to determine the
surface tension of a given liquid can be done as follows:
1. Clean the ring thoroughly before use.
2. Attach the ring to the lever arm.
3. Fill liquid sample in a vessel such as an evaporating dish, Petridish, or
beaker with a diameter of at least 4.5 cm to minimum depth of 1.0 cm.
4. Record the exact temperature.
5. Place the vessel on the sample table.
6.Raise the sample table assembly until the ring immersed
approximately 5 mm in the liquid.
7. Lower the sample table assembly until the ring is just below the surface
of the liquid.
8. Continue lowering the sample table assembly slowly until the ring is just
within the surface of the liquid. At this juncture, the reading on the
dial is still zero
9. Gradually increase the torsion of the wire while slowly lowering the
table. Continue this until the liquid film breaks and the ring breaks free.
10. The dial reading at the breaking point tothe liquid film isthe force of
the pull exerted on the ring, or the apparent surface tension.
11.This apparent surface tension must be adjusted by using acorrection
factor that accounts for the circumference of the ring, the size of wire
used in the ring, and the density of the liquid. This can be obtained from
the charts given literature.

OSPREADING COEFFICIENT

The concept of work of cohesion and work of adhesion help to

understand the spreading of one liquid on another and predict whether it
would spread spontaneously or not.
There exists a mathematicalrelationship, which can be used to forecast
the outcomeof the situation called as spreading coefficient, denoted by
S.

There are two possibilities, first, the liquid can spread over the surface of
sublayer liquid or second, the added liquid determining net loss in free
energy
If a force is applied on this liquid tube to separate into two parts, then
the work done is called the work of cohesion.

If aforce is applied to cause the liquids to separate, we have done three

things and the work done is called the work of adhesion (W,)
The spreading of liquid is controlled by surface tensions of pure
immiscible liquids and interfacial tension between them.
When a drop of liquid (oleic acid) is placed on the surface of water, it will
spread as a film if force of adhesion is greater than cohesive forces. This
phenomena isimportant in absorption of medicament from dosage form
E.g:- from cream or lotion.
For the stabilization of emulsion spreading coefficient phenomena is
useful.
 Now consider the hypothetical cylinder (cross-section area, 1 cm) of the
sublayer liquid Soverlaid with a similar section of the spreading liquid L.

L
L
Ya

S S

(a) (b)

Fig:- Representation of the work of adhesion invoBved in separating a

substrate and an overlying liquid
The work of adhesion = W, = Y+ Y -YLs (1)
Where,
YL and Y, are newly created surface tension and YLs interfacial tension that
has been destroyed in the process.
The work of cohesion, required to separate the molecules of the spreading
liquid so that it can flow over the sublayer. Here isno interfacial tension.
Now consider a hypothetical cylinder is divided two new surfaces are
created.
The work of cohesion = W, =2 YL (2)
1 m

L Y

(a) (b)

Fig :- Representation of the work of cohesion involved in separating like

molecules in a liquid.
 The work of adhesion is greater than the work of cohesion.
The spreading coefficient, S, is obtainedfrom Eqs. 1 &2
S=W,-W
(3)
(4)
" If, S is positive, it indicates
spreading and if negative indicates Air
no spreading.
" For the organic liquids spread on Lens
water, initial spreading coefficient
may be positive or negative, but the Lqud substrale
final spreading coefficient always
LS
negative.
* Initialspreading coefficient Sat20°
SUBSTANCE S(DYNEs/CM)
Ethyl alcohol 50.4

Propionic acid 45.8

Ethyl ether 45.5

Chloroform 13

Benzene 8.9

Hexane 3.4

Application ofspreading coefficientin Pharmacy:

a) Absorption of medicament from dermatological dosage form.
Ex:- Lotion,Cream
b) Stabilization of emulsion
c) Coating of the tablets
 JADSORPTIONAT LIQUID INTERFACES
The phenomenon of adsorption isthe adhesion of atom, ions, or molecules
from a gas, or liquid, a dissolved solid to the surface or interface
i. Gas/liquid interface
ii. Liquid/liquid interface
Theadsorption at the interface is of two types:
i) Positive adsorption
This is the adsorption when certain solute
molecules and ions when added to a liquid
are partitioned in favor of surface or the
interface.
The resulted in the increase in the
concentration of such molecules and ion at

the than inthe bulk of the liquid and lowersr

Fig:- Positive
the surface free tension
adsorbtion
This surface interface and interfacial
tension.

i) Negative adsorption
This is the adsorption
when certain molecules
like inorganic
electrolytes are

partitioned in favor of
bulk of the liquid.
This resulted in the in the
surface free energy and Fig :- Negative
adsorbtion
surface tension.
OSURFACE ACTIVE AGENTS
Molecules and ions that are adsorbed at the interface are termed surlace
active agents or surfactants.
Surfactants or amphiphiles have acertain affinity for both polar and
polar solvents.

Amphiphile may be hydrophilic (water -loving); lipophilic (oil- lovin

or well balanced between these two extremes. Ex: straight - chai
alcohols, amines and acids.
$ Types of surfactants
i. Anionic Surfactant

ii. Cationic Surfactant

ii.Non-ionicsurfactants
iv. Amphoteric Surfactants

i) Anionic Surfactants
Mostly anionic surfactants are those containing carboxylate, sulfonate and
sulfate ions.

Carboxylate ions are known as soaps and generally are prepared by the
saponification of natural acid glycerides in alkaline solution.

ii) Non-ionicSurfactants
Nonionic Surfactants do not ionize in aqueous solution, because their
hydrophilic group is of a non-dissociable type, such as alcohol, phenol,
ether, ester, or amide.
A large proportion of these nonionic surfactants are made of
hydrophilic portion (by the presence of a polyethylene glycol chain) and
lipophilic portion (alkyl or alkylbenzene)
iii) Cationic Surfactants
It includes long chain cations such as amine salts and quaternary
ammonium salts. Mostly used as antimicrobial preservatives.

iv) Amphoteric Surfactants

Those surfactants containing carboxylate or phosphate groups as the
anion, and amino or quaternary ammonium groups as the cation.
Zwitterionic (amphoteric) surfactants have both cationic and anionic
centers attached to the same molecule.

The anionic part can be variable and include sulfonates while cationic
part is based on primary, secondary, or tertiary amines or quaternary
ammonium cations.

Zwitterionic surfactants are often sensitive to pH and will behave as

anionic or cationic based on pH.

Typeof Surfactants Non-ionic group

Non-ionic
Wydrophobik group

Cationic
Cationic head

Anionic
Anionic head

Amphoteric
Zwitterionic head
 When a surfactant is dissolved in water at low concentration, a fraction
of it will be adsorbed at the air-water interface, and remainder will
reside in the bulk in the form of monomers.

As the concentration is increased 50 or more monomers come together

to form colloidal aggregates termed micelles.
The concentration at which aggregation occurs is called critical micelle
concentration or CMC.

" Surfactants are added in pharmaceutical preparations for various

purposes such as solubilizing agents, wetting agents, foaming agents,
suspending or emulsifying agentsetc.

Air
Partitioning
Water

Micellization

Amphiphilic molecule

Hydrophobic | Hydrophilic

Fig:- Critical micelle concentration

 OHLB SCALE
Griffin (1949) found a useful method for calculating balanced mixture of
emulsifying agents to form a stable emulsion.
Generally, each emulsifying agent has a hydrophilic portion and a
lipophilic portion.

18
Solubilizing agents (15-18)

15

Hydrophilic Detergents (13-15)

(water soluble)
12
Emulsitying agents (8-16)

Wetting and
Water
spreading agents (7-9)
dispersible

wlo Emulsifyingagents (3-6)

3
Hydrophobic Antifoaming agents (2-3)
(oil soluble)

Fig :- Ascale showing surfactant function on the basis of the HLB values.
Each portion might be more or less predominant resulting in providing
different types of emulsions.
Amethod has been devised to categorize emulsifying agents on the basis of
their hydrophile lipophile balance or 'HLB' Each emulsifying agent has
in polarity.
Ascale is framed called HLB scale, having values from 1 to 20.
 Synthetic emulsifiers
TYPE NAME OF EMULSIFIERS HLB
ANIONIC Glyceryl monostearate 11
Triethanolamine oleate 12
Sodium oleate 18
Potassium oleate 20
Sodium lauryl sulphate 40
CATIONIC Benzalkonium chloride 25-30
N-cetyl N-ethyl morpholiníum
Etho-sulphate
NONIONIC Sodium monooleate (span 80) 4.3
Sodium monolaurate (span 20) 8.6
Polyoxymethylene monostearate 11.1
(tween 60)
Polyoxymethylene sorbitan 15.0
monooleate (tween 80)
Polyoxymethylene sorbitan 16.7
monolaurate

* Required HLB value ofoils &wax

MATERIAL FOR W/0 FOR 0/W
Bees wax 4 12

Cetyl alcohol 15

Liquid paraffin 5 12

Soft paraffin 5 12

Woolfat 8 10

* Activity and HLB value ofsurfactants

ACTIVITY HLB

Antifoaming 1to 3
Emulsifier (w/o) 3to 6
Wetting agents 7 to 9

Emulsifiers (o/w) 8 to 18

Solubilizers 15 to 20

Detergents 13 to 15
DsOLUBILIZATION
This technique was introduced by Mc Bain in 1937.
It is the dissolution of poorly soluble solute molecules in water in
eof surfactants and forms thermodynamically stable solution.
The process of dissolution in presence of surfactants have been described
as the formation of micelles (colloidal aggregate of surfactant), which
ces the solubility of poorly soluble solute, when surfactant of proper
HLBis added in low concentration to liquid, it tends to orient at air
liquid interface.
Formation of micelles
a) Surfactant in low concentration
b) Surfactant in high concentration
c) Surfactant in the concentration of CMC

Surfactant Surfactant
Surfactant

Lquid

(e)
(b)
Liquid Micelle (c) Liquid
If surfactant is continued to be added in higher concentrations, air-liquid
interface is fully occupied, Figure (b).
At stillhigher concentrations, the surfactant molecules of ions are forced to
go into the bulk of the liquid, when the particular concentration of
surfactant molecule is maintained in the system, aggregates of
surfactants are formed called micelles, figure (c).
 The concentration of surfactant at which micelles formation takes place is

called critical micelle concentration (cmc).

Micelles may be of various shapes like:- spherical, sausage, rod or

lamellar.

Micelle formation increases the solubility of a solute by virtue of its

dissolving in or being absorbed onto the micelle.

This function of surfactant starts only at cmc and increases with the
concentration of the micelles.

As such cresol has only 2% v/v solubility in water but with soap solution

we can dissolve up to 50% v/v cresol in water (Lysol solution).

Polar end Water
of surtactant
Nonpolar end Cresol
of surfactant

Water

Creso

Water

Cresol

Fig - Lamellar micelles solubilize the cresol in water

The technique isuseful tosolubilize many water insoluble vitamins like A,
Dand Kand to prepare solutions of Chloroxylenol and Hexachlorophene.
 ODETERGENCY
Detergency is a complex process involving the removal of foreign
matter from surfaces.

Surfactants are used for the removal of dirt through the detergency
effect.

Initial wetting of the dirt and of the surface to be cleaned is carried out
by deflocculation and suspension or emulsification or solubilization of
the dirt particles.
It also involves foaming of the agent for entertainment and washing
away of the particles.
A wetting agent that when dissolved in water, lowers the advancing
contact angle, aids in displacing an air phase at the surface and replacing
it with a liquid phase.
Wetting agents are usefnlin :
i. Displacement of air from sulfur, charcoal and
The Tongue-Mucosllenbrane
other powders for dispersing these drugs in
liquid vehicles
ii. Displacement of air from the matrix of cotton
pads and bandages so that medicinal solutions
may be absorbed for application to various
body areas.
iüi. Displacement of dirt and debris using detergents in the washing of
wounds.

0v. The application of medicinal lotions and sprays to the surface of the

skin and mucous membrane

 OADSORPTIONAT SOLID INTERFACE
Thesubstance in adsorbed state is called adsorbate.
When adsorption occurs at the interface between liquid and solid, the
solid is usually called the adsorbent for gas-liquid interfaces sometimes
the liquid is called adsorbent.
> The adsorption process is generally classified as
i. Physisorption ii. Chemisorption
Solid-Gas Adsorption
" Solids adsorb gases to certain extent, but the phenomenon is not
prominent unless adsorbent possess large surface area.
The adsorptionof gas on toa solid surface is of mainly of two types.
i)Physisorption
Physisorption is the physical bonding of gas molecules to the surface
of a solid or liquid that the gas comes into contact with at low
temperatures.
This occurs due to Van der Waals forces.

The weak, long-range bonding is not surface specific and takes place
between all gas molecules on any surface.

Characteristics of physisorption
i. It is ageneral phenomenon and occurs in any solid/fluid systems.
ii. Minimum change in electronic state of adsorbate and adsorbent is
observed.

ii) Chemisorption
Chemisorption is an adsorption process that involves a chemical
reaction and that implies the formation of a covalent bond between the
molecule and one or more atoms on the surface.
 Characteristics ofChemisorption:
i. The phenomenon is characterized by chemical specificity.
i. Change in electronicstate may bedetectable by suitable physical means
(Eg:- UV, IR, microwavespectroscopy, conductivity etc.)
r Factors Affecting Adsorption
i) Surface area ofadsorbent
Being surface phenomena extent of adsorption depends on available
surface area of adsorbent.

Finely divided materials since has large surface area, more adsorption is
observed on their surfaces.
ii) Nature of adsorbate
The amount of adsorbate adsorbed on solids depends on its nature, easily
liquefiable gases adsorbed to greater extent.
ii) Temperature
As seen under the characteristics of physical adsorption, it decreases with
increase in temperature, while chemical adsorption increases with
increase in temperature.
iv) Pressure
Applying LeChatelier's principle, dynamic equilibrium exists between
adsorbed gas molecules and molecules in contact with adsorbate.
In fact,it isobserved that increase in pressure increases adsorption.
4 ADSORPTION ISOTHERMS
Adsorption isothernm is the relation between the quantity of adsorbate
adsorbed andthe partialpressure in the gas phase (or composition of bulk
phase, in adsorptions from liquids) under equilibrium conditions
constant temperature.
 Typesof Isotherms:
Types
of of Isotherms:
Amount
absorbate

Pressure Pressure Pressure Pressure Pressure

Typel Type-ll Type-!ll Type-N TypeV

Type-I
Langmuir and Freundlich isotherms are of Type-I where adsorption
takes place on non-porous solids.
It represents behaviour of nitrogen or oxygen on charcoal.
Total surface area can be determined from this isotherm by multiplying
the total number of molecules in the volume of gas adsorbed by the
cross-sectional area of the molecule.

º Type-II (BET EQUATION)

In this type of isotherm gases are physically adsorbed on a non-porous
solid forming monolayer followed by multilayer formation.
The first inflection in the curve represents formation of monolayer and
subsequent increase in pressure shows multilayer adsorption.
This isotherm is explained by BET (Branauer, Emmett and Teller)
equation.
 Pis pressure of the adsorbate
V y is mass of vapour per gram of adsorbent
Po isvapor pressure at saturation of adsorbent by adsorbate
y, is amount of vapour adsorbed per unit mass of adsorbent
bis constant

Type-I
This isotherm is rarely observed for example, bromine and iodine
silica gel., where heat of adsorption in the first layer is less than the
latent heat of condensation in the next layers.
The constant b of the BET equation is less than two.
>Type-IV
Thisisotherm is typical of adsorption onto porous solids where if the
first point is extrapolated to zero pressure represents the amount of gas
required in forming monolayer on solid surface.
Condensation within the capillaries is responsible for the further
adsorption.
The example of this type is adsorption of benzene on ferric oxide and
silica gel.
º Type-V
It is like type-III adsorption as capillary condensation is observed on
the porous solids for example, adsorption of water vaporon charcoal at
100°C.

<|E
lat constant T
Type-I
i. Freundlich isotherms P
P
i. Langmuir Freundlich adsorption Langmuir adsorption
isotherm isotherm
Ereundich's Adsorption Isotherm:
The scientist Freundlich's studied adsorption of gas on solid and from the
experimental data; he gave empirical equation called equation
Freudlich's adsorption isotherm,
W
y==kP 1/b
m

Where,

V y=Amount
= Adsorbate adsorbed by m gram of adsorbent at
equilibrium

P= Pressure and are determined from the experiment at

constant temperature.
V The constants k andb depends on nature of adsorbate and
adeorhant ac wallacon tanmnaratura
(wim)
adsorbed
Amount

Pressure
Fig:-Freundlich adsorption isotherm
 Langmuir Adsorption Isotherm:
In 1916,scientist Irving Langmuir (1916) published a new isotherm for
gasesadsorbed on solids, which retained his name.
It is an empirical isotherm derived from assumptions.
There certain assumptions on which Langmuir proposed his
theory, they are
i. Fixed number of vacant or adsorption sites are available on the
surface of solid.
ii. All the vacant sites are of equal size and shape on the surface of
adsorbent.

ii. Each site can hold maximum of one gaseous molecule and a constant
amount of heat energy is released during this process.
iv. Adsorption is monolayer or unilayer.
V. Dynamic equilibrium exists between adsorbed gaseous mnolecule and

the free gaseous molecules.

Langmuir had developed an equation based on the theory that the

molecules or atoms of gas are adsorbed on active sites of the solid to
form a layer one molecule thick.
If fraction of active centers occupied on surface of adsorbent by gas
molecules at pressure P is expressed as 0 then the fraction of sites
unoccupied is 1 - 0.
The rate of adsorption
(R,) = proportionalto unoccupied spots and the
/ P= pressure
(R) = The rate of evaporation of molecule bound on surface is
proportionalto the fraction of surface occupied, 6.
 R «fraction of sitesunoccupied x Pressure
R =k, (1- 0) P (1)
R,«Fraction of sites occupied
/ R =k, (2)
At equilibrium,
RË= Rz
k,(1 - 0) P =k, & -(3)
After rearranging equation
k,P
kztk,P
KP
K (4)
1+ K P

Replacing byy/ym and k,/k, by b.

Where,
y= ismass of gas adsorbed per gram of adsorbent at
P=pressure at constant temperature
Ym =mass of gas that adsorbed on 1 gram of adsorbent to forn
complete monolay
On substituting the values for and k,/k,the following equation
is obtained

bp (5)
ym 1+ bp

y=
bp (6)
1+bp
The equation (6)is known as Langmuir adsorption isotherm equation
and it can also be written in the following form.
P P (7)
+
y ymb Ym

200
150
Ply
100
50

10 20
Pressure

Fig :-Langmuir adsorption isotherm

By plotting a graph of P/y against P.
We get a straight line with slope equal to y, and intercept as b.

Applications ofadsorption
i. Adsorption of poisonous gases at the surface of mask. It is used by
the coal miners. Adsorption of traces of air to remove from the
devices.

ii. Adsorption of moisture in the medicine by silica gel pellets in order to

store in a controlled humidity.
üi. Adsorption of coloring agent by charcoal to get a clear solution.
iv. Adsorption of catalysts on reactants in order to increase the rate of
reaction