Surface and Interfacial Phenomena

Surface is a boundary between solid

or liquid phase and a vacuum.
Interface is a boundary between
two phases.
Surface free energy is the work
required to increase the area of the
surface by 1cm2.

Surface Tension is the force in dynes acting

along the surface of a liquid at right angle to
any line 1 cm in length.

= W/ A
where is the surface
tension , W is the work in erg required
to generate one square cm of surface
A.
The units of is either erg/cm2 or Dyne
/ cm
As an erg is equal to a dyne.cm
Surface tension is equal numerically and

The force of tension existing at the interface

between two immiscible liquids is known as
interfacial tension .
There are two forces that affect the behavior of
liquid on a solid:
1- Force of cohesion between the molecules of a
liquid.
2- Force of adhesion between the liquid and solid.
When the adhesion forces are stronger than the
cohesion forces ,the liquid spread over the solid.
e.g.water on glass.and the angle known as
contact angle is smaller than 90.And vice versa.

Factors affecting Surface Tension

1- Nature of the liquid.
2- Temperature : Surface tension decrease
with increase of temp.,i.e.with an
increase of kinetic energy of the
molecules.
= 0(1- T/Tc)1.2

3- Solute
The quantitative relationship between
solute distribution and surface
tension is expressed

Measurement of surface Tension

1- The capillary Rise Method:
r2hdg= 2r cos
= rhdg/2 or rhdg
2- The Drop weight Method:
mg= 2r
For relative measurement ,it easier to
determine the No of drops formed by a
given volume instead of determining the
weight of drops.
1/ 2 = n2d1/n1d2

3-Ring Method:
mg= 2 (r1+ r2)
Spreading coefficient (s).
S= Wa-Wc
S= s- (L+ LS)
Example : if the surface tension of water
is 72.8 dyne/cm , the surface tension of
benzene is 28.9 and interfacial tension
between them is 35.What is the initial
spreading coefficient ?
S = 72.8- (28.9+ 35) = 8.9 dyne/ cm.

Adsorption
Is the accumulation of a substance over
the surface of another substance.
e.g. Adsorption of alkaloid on charcoal.
Absorption
The penetration of a substance through
another substance.
e.g.water and sponge.

The Characteristics of Physical

Physical
Adsorption
and Chemisorption
Adsorption

1234-

weak physical forces.

Non specific.
Reversible.
Process is
exothermic.Amount of
adsorption decreases
with rise of temp.
5- More than one layer.
6- usually rapid at all
temp.

Chemisorption

1- Involve sharing of
electrons between
adsorbent and adsorbed
molecules .
2-non specific .
3- Irreversible.
4- Surface reaction only
proceeds above certain
temp.
5- Restricted to monolayer.
6-Rate increase rapidly by
increase temp.

Adsorption Isotherm
The relationship between the amount of
gas (adsorbate ) physically adsorbed
on a solid and equilibrium pressure or
concentration at constant temperature.
A- freundlich Adsorption Isotherm.
Y= x/m= kc1/n
Log x/m= log k + 1/n log c

B- Langmuir Adsorption Isotherm.

This equation is based on the theory that
the molecules of the gas are adsorbed
on active sites of the solid to form a
layer one molecule thick.
The fraction of the centers occupied by
gas at pressure P is .
The fraction of the sites not occupied is
1-
Rate of adsorption r1 = K1(1- ) P
Rate of evaporation r2 = K2
At equilibrium r =r

p/y = 1/b ym + p/ym

Factor Affecting Adsorption From
Solution :
1- Solute concentration
Adsorption is more complete from dilute
solution than from concentrated one.
2- Temperature:- the amount of
adsorption will decrease as the temp.
increase.
3- Surface area of adsorbent:- as
surface area increased the amount of
adsorption will increase.

5- Effect of Solvents:- adsorption of the solute

will be at maximum if the solvent is inert ( has
no affinity for adsorbent or for solute).
6- Removal of adsorbed impurities:- will
increase the amount of adsorption e.g.
activated charcoal .Heating it at 50-100 oc.
7- Adsorbent - solute interaction and
Solvent competition:- adsorption of a solute
from dilute solution involve breaking solute
solvent bond and adsorbent solvent bond and
formation of adsorbent solute bond. Selective
adsorption : charcoal will adsorb magenta dye
from solution however,if saponin is added to
the system the dyeis released since saponin is
preferentially adsorbed.

Application of adsorption in
pharmacy and allied field:1- Decolorizing agents. 2- Desiccant
and drying agents . 3- Adsorption
chromatography.
4- Medical adsorption. 5- Ion exchange.
Adsorbent materials:
Heavy kaolin, attapulgite ,bentonite ,
charcoal, diatomite , purified talc,
veegum, alumina, silica
Magnesium trisilicate ( florisil).

Surface Active Agents

SAA
Are solute that cause decrease in the
surface tension of the solvent.
All types of soluble SAA contain:
a- Lipophilic group
b- Hydrophilic group
A suitable balance between two opposing
groups of SAA is necessary to ensure
that surface active properties are
obtained.

Critical Micelle Concentration:- Is the

concentration of surfactant that form
micelle and at this concentration ,
dramatic changes in the
physicochemical properties of the
solution take place e.g. surface tension
, conductivity, osmotic pressure.
Classification of Surfactants:
They classified on the bases of :
1- Chemical structure
2-Uses to which they are put
3- physical propertis

Chemical classification of
surfactants:
Anionic Surface Active Agents :
a- Soaps
b- Organic sulfonate
c- Organic Sulfate
Cationic Surface Active Agents:
a- Quaternary Ammonium Salts
b- Pyridinium compounds

Non Ionic Surfactants:

Are classified according to the type of the
linkage between the hydrophilic group
and the lipophilic
group in the molecules into:
A- Ester linked surfactants.
b- Ether - linked surfactants.
c- Ester- ether linked surfactants.

Ampholytic Surface Active Agents:

2- Hydrophilic Lipophilic
Classification
(HLB) hydrophile lipophile balance
HLB value is the relative efficiency of the
hydrophilic portion of the surfactant
molecule to its lipophilic portion.
The HLB system act as a guide to
quantify all non ionic surfactants to
handful of general application.

Pharmaceutical Application of
Surfactants:
Wetting Agents
Emulsifying Agents
Solubilizing Agents
Foaming and Antifoaming
Detergents
Antibacterial Action of SAA.

Dissolution
Describe the process by which the drug
particles dissolve.
The dissolution of a drug is described in a
simplified manner by the Noyes Whitney
equation :
dm/ dt= kA(cs- c)
dm/dt is the dissolution rate.
K is the dissolution rate constant .
A is the surface area of dissolving solids .
Cs is the solubility of the drug .
C is the concentration of drug in the
dissolution medium at time t .

K which incorporating the drug diffusion

coefficient
And diffusion layer thickness. The
constant( k) is termed the intrinsic
dissolution rate and is a characteristic of
each solid drug compound in a given
solvent under fixed hydrodynamic
conditions.

Buffer solution and Buffer capacity

What is a buffer ?
What is the use of buffer in the field of
pharmacy?
pH= pka + log [A- ]/ [HA]
Buffer capacity( ) :- The ability of a buffer
to withstand the effect of acid and bases .
Buffer capacity is equal to the amount of
strong acid or strong base, expressed as
moles of H+ or oH- ions, required to change
the pH of one liter of the buffer by one pH
unit.

 It is clear that buffer capacity increases as the

concentrations of buffer components increases
The capacity is also affected by the ratio of the
concentration of weak acid and its salt.
Maximum capacity( max) is obtained when the
ratio of acid to salt = 1 i.e. pH = pka of the acid .
What is the characteristic of a suitable
buffer?
pKa value of the acid should be close to pH
required.
Its components must be compatible with other
ingredients in the system.
Toxicity of buffer components must be taken into
account if the solution is to be used for medical
purposes.

Colligative Properties
It is any physicochemical property of a
solution which depend only on the
number of dissolved particles and
not on the nature of those particles.
These include :
1- Vapor pressure lowering.
2- boiling point elevation.
3- Freezing point depression.
4- Osmotic pressure.

 Vapor pressure
The vapor pressure of the solution is
lower than of pure solvent. Why?
It can be explained by Raoult,s law
P= xsolv x po
Xsolv = mole fraction of solvent.
Po = vapor pressure of pure solvent.
Since Xsolv < 1 in any solution P < P0

Boiling Point :
When boiling occur?
As mentioned before the solute lower the
vapor pressure of the solvent . In order to
reach the atmospheric pressure ( boiling
point ) . It is necessary to increase
temperature.
Freezing Point:
The presence of solute molecules will interfere
with the formation of crystals of the solvent .
This change in the freezing process results in a
depression of the freezing point for the
solution relative to the pure solvent.

Osmotic Pressure:
Osmotic pressure of the solution is the external
pressure that must be applied to the solution to
prevent it being diluted by the entry of solvent via a
process that is known as Osmosis.
This process refers to the spontaneous diffusion of
solvent from a solution of low solute concentration
( or pure solvent) into a more concentrated one
through a semi permeable membrane. Such a
membrane separate the two solutions and is
permeable only to the solvent molecules.
This process occurs spontaneously at constant
temperature and pressure.

Rate and order of reaction:

The rate of a chemical reaction or
process is the velocity with which it
occurs.
Order of reaction refers to the way in
which the concentration of drug or
reactant influences the rate of a
chemical reaction or process.
Zero order reaction :
If the amount of a drug A is decreasing
at a constant time interval t , then the
rate of disappearance of drug A is

Where Ko is the zero order rate constant and its unit

is mass/ time ( e.g. mg/min).
Integration of equation yield the following
expression
A = Kot+ Ao where Ao is the amount of drug at time
t=zero.
First order reaction :
If the amount of the drug A is decreasing at a rate
that is proportion to the amount of drug A
remaining , then the rate of disappearance of drug
is expressed as follow:
dA/dt= - kA where k is first order rate constant and
is expressed in unit time -1 .

Complex Reactions include

1-opposite or reverse reaction
2- consecutive reaction
3- Side reaction
Along with main reaction .
Reversible reaction :
A--------------B
A--------------B+ C
A+B------------- C+D this reaction is
example of second order reaction

e.g. is the reaction between acid and alcohol to form

ester and water .
CH3CooH+ C2H5OH--------------CH3CooC2H5 +H2O
The rate of reaction is proportion to the concentration of
two reacting substance A and B in the forward reaction
and C and D in the reverse reaction .
If a and b represent the initial concn. Of two reacting
substances and if x denote the moles of A and B in each
liter reacting in interval of time t
The velocity of reaction is expressed by this
equation :
dx/ dt= K (a-x) (b-x)
(1) when a not equal b
If a=b
dx/ dt= K(a-x)2
(2)

Integration of equation (1)will yield :

K= 2.303/ t(a-b)log b(a-x)/a(b-x)
K can be determined by plotting t against
2.303/a-b log b(a-x)/a(b-x)
The slope of the line equal K
The unit for second order rate constant K is
concentration -1time-1.
Integration of equation( 2) will yield:
K = 1/t.x/a(a-x) and k can be determined by
plotting t against x/ a(a-x) the slope of the
line = k and half life (t1/2) for the second
order decomposition that obey this equation
t1/2 = 1/aK