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Surface and
Interfacial
phenomena
 The boundary that forms between two phases like
solid and liquid is called interface.
 Surface Tension: it is defined as the force, in
dynes, acting on the surface of the liquid at right
angles to any line of length of surface, 1
centimeter.
 Interfacial tension: It is defined as the force per
unit length parallel to the interface to counter
balance the net inward pull.
 Cohesive forces: Intermolecular attraction between
like molecules called cohesive forces.
 Adhesive forces: Attraction between unlike
molecules are called adhesive forces.
 SURFACE TENSION:
 The unit of surface tension is dy/cm (CGS System) and
Newton/ meter in MKS system.
the phenomenon of surface tension is responsible for the
following processes
 Formulation of spherical globules in emulsion.
 Formation of nearly spherical shape of falling water
droplets.
 Formation of spherical shape of mercury particles on a
flat surface .
 Rise of liquid in a capillary tube.
 It is also important physicochemical property and a
characteristics of a liquid.
A number of methods are available to determine
surface and interfacial tension:
 Capillary rise.
 Tensiometer.
 Drop weight method.
 Drop count method.
Capillary Rise Methods
 When a capillary tube is placed in the liquid contained
in a beaker, the liquid rises up in the tube to a certain
distance.
 This is because the adhesive forces between the liquid
molecules.
 The glass are stronger than the cohesive forces between
liquid molecules.
 The rise in the tube continue until the upward
movement is just balanced by the down-ward force of
gravity due to the weight of the liquid.
Example:
 Underground water rising on to the surface.
 Oil rising through wick in a lamp.
 To certain extent, water rising from soil to the branches
above the ground in plants.
Derivation:
 Upward component:
this force represents the surface tension of liquid (γ) at any
point on the circumference.
This is given by the equation…………….
Upward component,
 a = γ . Cos θ --------- (1)
Where, γ = surface tension of the liquid.
θ = contact angle between the surface of the liquid and
capillary wall
The total upward force around the inside circumference (2 π r)
of the tube
Up ward component :
a = γ . 2 π r. Cos θ ------------- (2)
Where, r = inside diameter of the capillary tube.
For water θ = 0, because water completely wets the capillary
wall.
The contact angle is very small Cos θ = 1
so the, Up ward component,
a = γ . 2 π r -------------- (3)
 Downward Component:
the counteracting force is gravity and depends on the
weight of liquid in the capillary rice.
Downward component,
b = mass of the liquid in capillary X acceleration
= volume X density X acceleration
= cross-section area X height X density X acceleration
= π r2. h .ρ .g ----------------- (4)
At the equilibrium,
upward component = downward component
γ . 2 π r = π r2. h .ρ .g ------------------ (5)
γ = ½ r h .ρ .g ------------------- (6)
This equation is used to estimate the surface tension of
liquids by the capillary rise methods.
Surface Active Agent
 Molecules and ions that are adsorbed at the
interface are called surface active agent or
surfactant.
 Surface active agent reduce the interfacial tension.
 Surface active agents are polymer like substances
which have both polar and non polar group.
 Surface active agents are amphiphiles.
 Amphiphiles are molecules or ions which have certain
affinity for both polar and nonpolar solvent.
 In water, at low concentration surface active agents exist
individually as monomers.
 As concentration increases, the monomers aggregate
themselves over a narrow range of concentration.
 These aggregates are called as micelles.
 Each micelle may contain around monomers and size may
be about 50 A.
 Critical micelle concentration is defined as the
concentration range of a surfactant at which micelles
start formation.
 Amphiphiles are molecules or ions which have a certain
affinity for both polar and nonpolar solvent.
 The hydrocarbon chain is designated as the tail and polar
portion is indicated by head.
 Below the CMC surface active agents get adsorbed at air
water interface.
 As the concentration of surfactant increases, molecules
get accumulated progressively at the interface.
 the formation of micelles is so spontaneous that it
is difficult to differentiate the concentration related
to saturated phase and micelle phase.
 Example of surface active agents are: sodium
lauryl sulphate, cetyl trimethyl ammonium
bromide, polyoxethylene lauryl ether. etc
Application of Surface active agent:
 Pharmaceutical adjuvants: They are added to
the drugs in order to improve the product
characteristics in the design of dosage forms in a
variety of ways
Solubilizing agents, wetting agents, detergents,
suspending agents, emulsifying agents, Foaming
agents.
 Influence on drug action: Surfactants at low
concentrations enhance the penetration of
Hexylresorcinol into the pinworm, Ascaris.
They reduce the interfacial tension between the
liquid phase and the cell wall of the organism.
 Antibacterial activity: ionic surfactants adsorbed on the
cell surface by electrostatic interaction.
 As a result, cell surface loos its integrity and the essential
materials are lost through the leaks.
 Thus the antibacterial action is observed
Surface Free Energy
 Surface free energy is defined as the work required to
increase the area of a liquid by 1 sq cm.
 As per the definition, surface free energy is equal to
the surface tension.
Estimation of Surface free Energy
 ABCD is a rectangular wire. The side of AD = L.
 L is movable.
 A drop of soap solution is placed on the frame, so that
it forms a film within the frame.
 The side AD remains stable on account of surface
tension exerted by the soap film.
 When the force is applied downward, the film gets
stretched as the movable bar AD goes down until the
film breaks.
 If force ‘f’ is applied on AD ( Downward
component), it shifts the movable wire to a distance ‘d’
to A’ D’.
 The work done ‘W’ is given by
Work done (W) = force X distance moved
W = f X d
 The above force acts against the surface tension
(upward component) ‘γ’ of the liquid
 Again f = γ X 2L
 Where L = length
 Substituting the equation it gives
 W = γ X 2L X d
 2L x d is equal to increase in surface area ‘ΔA’
Produced by extending the soap film, so the equation is
W = γ X ΔA
ΔG = γ X ΔA
W = Work done.
ΔG = Surface free energy
Hydrophilic lipophilic Balance (HLB)
 HLB is an arbitrary scale that indicates the extent of
hydrophilic lipophilic balance.
 Surfactant such as Spans ( Sorbitan ester) are lipophilic
and have low HLB value ( 1.8 to 8.6)
 Tweens ( poly-oxy-ethylene derivatives of Span) are
hydrophilic and have high HLB values ( 9.6 to 16.7).
 The higher the HLB of an agent, the more the
hydrophilicity.
 A HLB value of 1 implies that it is soluble in oil.
 HLB value 20 implies that it is soluble in water.
Method Of Estimation
Method I :
 the structure of a surfactant molecules is split into
different component groups.
 Each group is assigned a number.
 The addition of these numbers for their respective
groups permits the calculation of its HLB value.
HLB = ∑ ( hydrophilic group number) - ∑ ( lipophilic
group number) + 7
 Method 2 : In this method, each atom or group has
been assigned a constant.
 Example: when a surfactant contains
polyoxyethelenr chains,
 The HLB value can be estimated by the formula
HLB = E + P / 5
Where, E = % weight of ethylene oxide chains.
P = % weight of polyhydric alcohol groups.
 Method 3 : If surfactant contains ester functional
groups, such as glyceryl monostearate, the HLB
value can be estimated using the formula
HLB = 20 ( 1- S / A)
S = Saponification number of the ester.
A = Acid number of the fatty acid.
 Disadvantages of the HLB Systems:
 1. this system provides information regarding the
nature of the surfactant used, but the concentration of
such surfactant is equally important.
 The HLB system neglects the concentration of
surfactant required for the optimum stability of
emulsion.
 through HLB of a surfactant indicates the solubility
properties, it is an over-simplification.
 It cannot be always realistic. Because solubility
depends on the nature of the solvent, temperature and
presence or absence of additives.
Adsorption At Liquid Interfaces
 Certain molecules or ions when added to a liquid,
they may modify the interface in different ways.
 When the added molecules move on their own
accord to the interface, this process is called
positive adsorption or adsorption.
Adsorption at Solid Interface
 Adsorption of a gas or a liquid onto a solid surface is
important in pharmacy. The material used to adsorbed
gases or liquids is termed as adsorbent.
 the substance that is attached to the surface of the solid
is called adsorbate.
 The degree of adsorption of gas by a solid depends on
the
1. nature of adsorbent and its surface area.
2. nature of adsorbate and the partial pressure of gas.
3. temperature.
 Depending on the nature of interaction, Adsorption is
classified into physical adsorption and chemical
adsorption.
Detergency
 Surfactants in aqueous solutions are used to remove
the dirt from substrates such as glass, fabric, skin etc.
 Effective detergents are required for the cleaning of
production equipment, containers for packing and
maintain hygiene in the industry.
Steps of DETERGENCY are:
 Initial wetting of the dirt from the surface.
 Solubilizing of the dirt.
 Removing the insoluble dirt as deflocculating particles.
 Suspending the particles in the detergent solution.
 Removing the oil soluble materials and convert into
emulsion.
 Converting the dirt into foam so as wash easily.
 The HLB requirement for the detergency is about 13 to
16
 Examples:
Cationic type: Cetrimide ( cetyltrimethyl ammonium
chloride).
Anionic Type: Soaps, Sodium lauryl sulphate.
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surface_and_interfacial_phenomena.pdf

  • 2.  The boundary that forms between two phases like solid and liquid is called interface.
  • 3.  Surface Tension: it is defined as the force, in dynes, acting on the surface of the liquid at right angles to any line of length of surface, 1 centimeter.  Interfacial tension: It is defined as the force per unit length parallel to the interface to counter balance the net inward pull.  Cohesive forces: Intermolecular attraction between like molecules called cohesive forces.  Adhesive forces: Attraction between unlike molecules are called adhesive forces.
  • 4.  SURFACE TENSION:  The unit of surface tension is dy/cm (CGS System) and Newton/ meter in MKS system. the phenomenon of surface tension is responsible for the following processes  Formulation of spherical globules in emulsion.  Formation of nearly spherical shape of falling water droplets.  Formation of spherical shape of mercury particles on a flat surface .  Rise of liquid in a capillary tube.  It is also important physicochemical property and a characteristics of a liquid.
  • 5. A number of methods are available to determine surface and interfacial tension:  Capillary rise.  Tensiometer.  Drop weight method.  Drop count method.
  • 6. Capillary Rise Methods  When a capillary tube is placed in the liquid contained in a beaker, the liquid rises up in the tube to a certain distance.  This is because the adhesive forces between the liquid molecules.  The glass are stronger than the cohesive forces between liquid molecules.  The rise in the tube continue until the upward movement is just balanced by the down-ward force of gravity due to the weight of the liquid.
  • 7. Example:  Underground water rising on to the surface.  Oil rising through wick in a lamp.  To certain extent, water rising from soil to the branches above the ground in plants.
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  • 9. Derivation:  Upward component: this force represents the surface tension of liquid (γ) at any point on the circumference. This is given by the equation……………. Upward component,  a = γ . Cos θ --------- (1) Where, γ = surface tension of the liquid. θ = contact angle between the surface of the liquid and capillary wall The total upward force around the inside circumference (2 π r) of the tube
  • 10. Up ward component : a = γ . 2 π r. Cos θ ------------- (2) Where, r = inside diameter of the capillary tube. For water θ = 0, because water completely wets the capillary wall. The contact angle is very small Cos θ = 1 so the, Up ward component, a = γ . 2 π r -------------- (3)
  • 11.  Downward Component: the counteracting force is gravity and depends on the weight of liquid in the capillary rice. Downward component, b = mass of the liquid in capillary X acceleration = volume X density X acceleration = cross-section area X height X density X acceleration = π r2. h .ρ .g ----------------- (4) At the equilibrium, upward component = downward component
  • 12. γ . 2 π r = π r2. h .ρ .g ------------------ (5) γ = ½ r h .ρ .g ------------------- (6) This equation is used to estimate the surface tension of liquids by the capillary rise methods.
  • 13. Surface Active Agent  Molecules and ions that are adsorbed at the interface are called surface active agent or surfactant.  Surface active agent reduce the interfacial tension.  Surface active agents are polymer like substances which have both polar and non polar group.  Surface active agents are amphiphiles.
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  • 15.  Amphiphiles are molecules or ions which have certain affinity for both polar and nonpolar solvent.  In water, at low concentration surface active agents exist individually as monomers.  As concentration increases, the monomers aggregate themselves over a narrow range of concentration.  These aggregates are called as micelles.  Each micelle may contain around monomers and size may be about 50 A.
  • 16.  Critical micelle concentration is defined as the concentration range of a surfactant at which micelles start formation.  Amphiphiles are molecules or ions which have a certain affinity for both polar and nonpolar solvent.  The hydrocarbon chain is designated as the tail and polar portion is indicated by head.  Below the CMC surface active agents get adsorbed at air water interface.  As the concentration of surfactant increases, molecules get accumulated progressively at the interface.
  • 17.  the formation of micelles is so spontaneous that it is difficult to differentiate the concentration related to saturated phase and micelle phase.  Example of surface active agents are: sodium lauryl sulphate, cetyl trimethyl ammonium bromide, polyoxethylene lauryl ether. etc
  • 18. Application of Surface active agent:  Pharmaceutical adjuvants: They are added to the drugs in order to improve the product characteristics in the design of dosage forms in a variety of ways Solubilizing agents, wetting agents, detergents, suspending agents, emulsifying agents, Foaming agents.  Influence on drug action: Surfactants at low concentrations enhance the penetration of Hexylresorcinol into the pinworm, Ascaris. They reduce the interfacial tension between the liquid phase and the cell wall of the organism.
  • 19.  Antibacterial activity: ionic surfactants adsorbed on the cell surface by electrostatic interaction.  As a result, cell surface loos its integrity and the essential materials are lost through the leaks.  Thus the antibacterial action is observed
  • 20. Surface Free Energy  Surface free energy is defined as the work required to increase the area of a liquid by 1 sq cm.  As per the definition, surface free energy is equal to the surface tension.
  • 21. Estimation of Surface free Energy  ABCD is a rectangular wire. The side of AD = L.  L is movable.  A drop of soap solution is placed on the frame, so that it forms a film within the frame.  The side AD remains stable on account of surface tension exerted by the soap film.  When the force is applied downward, the film gets stretched as the movable bar AD goes down until the film breaks.
  • 22.  If force ‘f’ is applied on AD ( Downward component), it shifts the movable wire to a distance ‘d’ to A’ D’.  The work done ‘W’ is given by Work done (W) = force X distance moved W = f X d  The above force acts against the surface tension (upward component) ‘γ’ of the liquid  Again f = γ X 2L  Where L = length  Substituting the equation it gives  W = γ X 2L X d
  • 23.  2L x d is equal to increase in surface area ‘ΔA’ Produced by extending the soap film, so the equation is W = γ X ΔA ΔG = γ X ΔA W = Work done. ΔG = Surface free energy
  • 24. Hydrophilic lipophilic Balance (HLB)  HLB is an arbitrary scale that indicates the extent of hydrophilic lipophilic balance.  Surfactant such as Spans ( Sorbitan ester) are lipophilic and have low HLB value ( 1.8 to 8.6)  Tweens ( poly-oxy-ethylene derivatives of Span) are hydrophilic and have high HLB values ( 9.6 to 16.7).  The higher the HLB of an agent, the more the hydrophilicity.  A HLB value of 1 implies that it is soluble in oil.  HLB value 20 implies that it is soluble in water.
  • 25. Method Of Estimation Method I :  the structure of a surfactant molecules is split into different component groups.  Each group is assigned a number.  The addition of these numbers for their respective groups permits the calculation of its HLB value. HLB = ∑ ( hydrophilic group number) - ∑ ( lipophilic group number) + 7
  • 26.  Method 2 : In this method, each atom or group has been assigned a constant.  Example: when a surfactant contains polyoxyethelenr chains,  The HLB value can be estimated by the formula HLB = E + P / 5 Where, E = % weight of ethylene oxide chains. P = % weight of polyhydric alcohol groups.
  • 27.  Method 3 : If surfactant contains ester functional groups, such as glyceryl monostearate, the HLB value can be estimated using the formula HLB = 20 ( 1- S / A) S = Saponification number of the ester. A = Acid number of the fatty acid.
  • 28.  Disadvantages of the HLB Systems:  1. this system provides information regarding the nature of the surfactant used, but the concentration of such surfactant is equally important.  The HLB system neglects the concentration of surfactant required for the optimum stability of emulsion.  through HLB of a surfactant indicates the solubility properties, it is an over-simplification.  It cannot be always realistic. Because solubility depends on the nature of the solvent, temperature and presence or absence of additives.
  • 29. Adsorption At Liquid Interfaces  Certain molecules or ions when added to a liquid, they may modify the interface in different ways.  When the added molecules move on their own accord to the interface, this process is called positive adsorption or adsorption.
  • 30. Adsorption at Solid Interface  Adsorption of a gas or a liquid onto a solid surface is important in pharmacy. The material used to adsorbed gases or liquids is termed as adsorbent.  the substance that is attached to the surface of the solid is called adsorbate.  The degree of adsorption of gas by a solid depends on the 1. nature of adsorbent and its surface area. 2. nature of adsorbate and the partial pressure of gas. 3. temperature.
  • 31.  Depending on the nature of interaction, Adsorption is classified into physical adsorption and chemical adsorption.
  • 32. Detergency  Surfactants in aqueous solutions are used to remove the dirt from substrates such as glass, fabric, skin etc.  Effective detergents are required for the cleaning of production equipment, containers for packing and maintain hygiene in the industry.
  • 33. Steps of DETERGENCY are:  Initial wetting of the dirt from the surface.  Solubilizing of the dirt.  Removing the insoluble dirt as deflocculating particles.  Suspending the particles in the detergent solution.  Removing the oil soluble materials and convert into emulsion.  Converting the dirt into foam so as wash easily.  The HLB requirement for the detergency is about 13 to 16
  • 34.  Examples: Cationic type: Cetrimide ( cetyltrimethyl ammonium chloride). Anionic Type: Soaps, Sodium lauryl sulphate.