Download - Interfacial phenomena
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Interfacial PhenomenaAna Marie L. Rubenicia,RPh
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Interfacial Phenomena
When phases exist together, the boundary between two of them is termed an interface.
The properties of the molecules forming the interface are often sufficiently from those in the bulk of each phase that they are referred to as forming an interfacial phase.
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Interfacial Phenomena
SURFACE TENSION INTERFACIAL TENSION
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Interfacial Phenomena
Several types of interface can exist, depending on whether the two adjacent phases are in the solid, liquid or gaseous state.
For convenience, we shall divide these various combinations into two groups, namely liquid interfaces and solid interfaces.
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Interfacial Phenomena
Importance I Pharmacya.Adsorption of drugs onto adjuncts in
dosage forms.b.Penetration of molecules through
biological membranes.c.Emulsion formation and stability.d.Dispersion of insoluble particles in
liquid media to for suspensions.
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Interfacial PhenomenaClassification of
Interfaces
Solid-solid interface, powder particles in contact.ySS
Solid - solid
Liquid-solid interface, suspensionyLS
Liquid - solid
Liquid-liquid interface, emulsionyLL
Liquid - liquid
Solid surface, table topySV
Gas - solid
Liquid surface, body of water exposed to atmosphereуLV
Gas - liquid
No interface possible-Gas - gas
Types & Examples of InterfaceInterfacial Tension
Phase
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Liquid InterfacesSurface and Interfacial Tension
Surface The term surface is customarily used
when referring to either a gas-solid or a gas-liquid interface.
“Every surface is an interface.”
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Liquid Interfaces
Surface tension- a force pulling the molecules of the interface together resulting in a contracted surface.
- Force per unit area applied parallel to the surface.Unit in dynes/cm or N/m
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Liquid Interfaces
Interfacial tension Is the force per
unit length existing at the interface between two immiscible liquid phases and like surface tension, has the units of dyne/cm..
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Liquid Interfaces Surface Free
energy – increase in energy of the liquid and the surface of the liquid increase.
-work must be done to increase liquid surface.
γ – surface tension or surface free energy per unit surface.
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Liquid Interface Surface Free energy
W = γ ∆ A where W is work done or surface free energy increase
expess in ergs(dynecm); γ is surface tension in dynes/cm and ∆ A is increase in are in cm sq.
What in the work required to increase area of a liquid droplet by 10 cm sq if the surface tension is 49 dynes/cm?W = 49 dynes/cm x 10 cm sq = 490 ergs
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Liquid InterfacesMeasuring Surface and Interfacial Tension
1. Du Nouy Ring Method This method also is called the detachable ring method and
is used to measure both the l surface tension and interfacial tension. It employs a tensiometer that consists of a hanging platinum-indium ring of defined geometry connected with a microbalance. to the surface tension y of the liquid.
2. Capillary Rise Method If a capillary tube is placed in a liquid that wets the surface of the capillary, the liquid will rise inside the capillary tube and its surface will be concave.
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Liquid Interfaces When oleic acid is
placed on the surface of a water , a film will be formed if the force of adhesion b/n oleic accid molecules and water molecules is greater than the cohesive forces b/n the oleic acid molecules themselves.
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Liquid Interfaces Work of adhesion(Wa), which is the energy
required to break the attraction between the unlike molecules.(water to oil)
Work of cohesion(Wc), required to separate the molecules of the spreading liquid so that it can flow over the sublayer.(oil to oil and water to water)
Spreading of oil to water occurs if the work of adhesion is greater than the work of cohesion.
Spreading coefficient(S) – difference between Wa and Wc.
Positive S – if oil spreads over a water surface.
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Liquid InterfacesSurface and Interfacial Tension
When a drop of oil is added on the surface of water, three things may happen:
1. The drop may spread as a thin film on the surface of water.(positve S)2. It may form a liquid lens if the oil cannot spread on the surface of water.(negative S)3. The drop may spread as a monolayer film with areas that are identified as lenses.
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Liquid Interfaces Organic liquids on water are unstable Effects og Molecular Structure on Spread
Coefficient(S)a. Polar groups such as COOH or OH such as propionic acid and ethanol have high values of S.b. Increase in carbon chains of acids will lead to decrease of polar-nonpolar char ratio thus decrease in S on water. Ex are nonpolar liq petrolatum fail to spread on water.
Benzene spreads in water because of its weak cohesive forces.
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Liquid Interfaces
For lotions with mineral oil base to spread freely and evenly on the skin , its polarity and spreading coefficient should be increase by the addition of surfactants.
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Liquid Interfaces
50.445.845.545.242.4
32 (250)24.6138.93.4
0.22-3.19-13.4
Ethyl alcohol
Propionic acid
Ethyl ether
Acetic acid
Acetone
Undecyclenic acid
Oleic acid
Chloroform
Benzene
Hexane
Octane
Ethylene dibromide
Liquid petrolatum
S (dynes/cm)Substance
Initial Spreading Coefficients, S, at 20◦ C
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Interfacial Phenomena
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Interfacial PhenomenaApplication of Surface Active Agents
In addition to the use of surfactants as emulsifying agents, detergents, wetting agents and solubilizing agents, they find application as antibacterial and other protective agents and as aids to the absorption of drugs in the body.
A surfactant may affect the activity of a drug or may itself exert drug action.
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Interfacial PhenomenaApplication of Surface Active Agents
Foams and Antifoaming agents
© Any solutions containing surface-active materials produce stable foams when mixed intimately with air. A foam is relatively stable structure consisting of air pockets enclosed within thin films of liquid, gas-in-liquid dispersion stabilized by a foaming agent. The foam dissipates as the liquid drains away from the area surrounding the air globules, and the film finally collapses.
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Interfacial PhenomenaApplication of Surface Active Agents
Agents such as alcohol, ether, castor oil, and some surfactants may be used to break the foam and are know as antifoaming agents.
Foams are sometimes useful in Pharmacy but are usually nuisance and are prevented or destroyed when possible. The undesirable foaming of solubilized liquid preparations poses a problem in formulation.
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Interfacial Phenomena
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Interfacial PhenomenaElectric Properties of Interfaces
The Electric Double Layer
Consider a solid surface in contact with a polar solution containing ions, for example, an aqueous solution of electrolyte.
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Interfacial PhenomenaElectric Properties of Interfaces
Nernst and Zeta Potentials
- The potential at the solid surface aa’, due to the potential determining ion, is the electrothermodynamic (Nernst) potential, E, and is defined as the difference between the actual surface and the electroneutral region of the solution.
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Interfacial PhenomenaElectric Properties of Interfaces
The potential located at the sheer plane bb’ is known as the electrokinetic, or zeta potential. The zeta potential is defined as the difference in potential between the surface of the tightly bound layer (shear plane) and the electroneutral region of the solution.
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Interfacial PhenomenaElectric Properties of Interfaces
Zeta potential has practical application in the stability of systems containing dispersed particles, since this potential, rather than the Nernst potential governs degree of repulsion between adjacent, similarly charged, dispersed particles.
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Adsorption at Liquid Interfaces
Occurs at the surface or interfaces of liquids
Surface Active Agents/ Surfactants/ Amphifiles
•Substances with part of their molecule lipophilic and part hydrophilic move on their own to the surfaces or interfaces of the liquid, where they lower the surface or interfacial tension
•The dual character of their molecule[hydrophilic & lipophilic]
•Often represented in a graphic form as a circle with a tail
Circle- Hydrophilic part or the polar part
Tail- lipophilic or the non-polar part
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Micelles
Are formed when the active molecules saturate the surface of the water
Often spherical; but may also come in different forms
Cationic-cations
Anionic-anion
Amphoteric-amphoteric ions
Nonionic-nonions
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Hydrophile- Lipophile Balance [HLB]
The number that describes and makes possible to organize info about the hydrophilic-lipophilic nature of the surface active molecule
An arbitrary scale which was developed by GRIFFIN in 1949
Davis and Rideal23 formula:
HLB= Σ[Hydrophilic group #] – Σ[lipophilic group #]+7
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HLB Value
Use
0-3
4-6
7-9
8-18
13-15
10-18
Antifoaming agents
W/O emulsifying agents
Wetting agents
O/W emulsifying agents
Detergents
Solubilizing agents
Trial and error The combination of the surface active agents has a new HLB
value equal to the algebraic mean of both HLB values:HLBmixture= ƒHLB1
+(1-ƒ)HLB2
Where ƒ is the fraction of surfactant 1 and the fraction of surfactant 2 is (1-ƒ)
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Monolayers at the Surfaces
• Substances that reduces the surface tension of a liquid
Gibbs Adsorption Equation:
Where: Γ=Surface concentration in moles per unit area of surface C=concentration of the substance γ= surface tension R= gas constant T= temperature
/ C= change in the surface tension
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Example
The concentration of a surfactant in water is 0.01 mole/L, and dγ/dC is –5.87 dyne liter mole-1 cm-1. What is the surface concentration of the surfactant at 20ºC?
Solution:
Γ= (0.01 mole/L)
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Critical Micelle Concentration [CMC]
Shows that the surface tension decreases with increasing concentrations of the surface active agent then after a certain concentration of the surface active agent, the surface tension stops decreasing and reaches a plateau.
The surface is saturated with surface active molecules and any inc in their conc will cause them to form micelles in the bulk to protect their hydrophobic groups from the aqueous envt.
In aqueous media, decreases as the # of carbons in the hydrophobic grp of the surface active agent increases
Decreases with electrolytes in soln
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Critical Micelle Concentration [CMC] Molecules can form aggregates in which the
hydrophobic portions are oriented within the cluster and the hydrophilic portions are exposed to the solvent. Such aggregates can show a variety of conformations. The shapes of the aggregates depends largely of the properties of the amphiphilic molecules.
The proportion of molecules present at the surface or as aggregates in the bulk of the liquid depends on the concentration of the amphiphile. At low concentrations amphiphiles will favor arrangement on the surface. As the surface becomes crowded with amphiphiles more molecules will arrange into aggregates. At some concentration the surface becomes completely loaded with amphiphile and any further additions leads to arrangement into aggregates. This concentration is called the Critical Micelle Concentration(CMC). A graph of surface tension vs log of concentration may be used to determine the CMC point.
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Tilted-drop Measurement• The tilted-drop measurement (Fig. 2e) is another angle measurement. In
this technique, a droplet is added to the surface and the advancing and retreating contact angle are measured as the surface is tilted up until the droplet reaches a point where it almost moves. This technique is useful to measure both the receding and advancing contact angles at the same time.
• In general, contact angle measurements serve as a good initial technique to characterize a surface. However, contact angle measurements need to be analyzed with care as a number of factors including operator error, surface roughness, surface heterogeneity, contaminated fluids, and sample geometry can influence the overall result.
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Figure 1 Figures 1A and 1B demonstrate a difference in wettability. Figure 1A shows how a water droplet might appear on a hydrophobic surface such as wax. Figure 1B shows how a water droplet might appear on a hydrophilic surface such as a contact lens
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Figure 2. Five ways that the contact angle (q) can be measured. (A.) Sessile or Static drop. (B.) Wilhelmy plate method. (C.) Captive air bubble method. (D.) Capillary rise method. (E.) Tilting substrate method. Figure adapted from Ratner, et. al.
Figure 3. A generalized contact angle plot showing the advancing (qAdv) and receding (qRec) contact angles.
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The concentration of the surface active agent affects:
a. Interfacial tensionb. Osmotic pressurec. Detergency[ability to remove soil]d. Light scatteringe. Solubility
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Interfacial Tension
Follows a path parallel to that of the surface tension
Decreases with increasing concentration of the surface active agent until the CMC is reached, then becomes constant
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Osmotic Pressure
Increases as the surface active agent increases
But at CMC it reaches a plateau
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Detergency, Solubility, Light Scattering Ability
Increases sharply when the concentration of the surface active agent increases beyond the CMC concentration.
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MicelLes
Are aggregates of surface active agents
Size varies, but is more than 0.1μm # of molecules is approximately 50-
100 Are always in equilibrium with
monomers of surface active agents in soln
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Surface Active Agents
Hydrophilic and lipophilic Reside at interfaces and lower the
interfacial tension Can be synthetic or natural Anionic, cationic,nonionic and
zwitterionic
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Anionic Surface Active Agents Has a negative charge Widely used in the pharmaceutical and
cosmetic industries Have an unpleasant taste Have skin irritation potential Not compatible with cationic surface
active agents Compatible with nonionics and
zwitterionic surface active agents
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Types of Anionic Surface Active Agents
SOAPS-fatty acid chain ranges between 12-18
Sulfates-most popular Toothpaste,shampoos and other cosmetic products as well as
in fabric detergents
Sulfonates-sulfur atom connected to the carbon atom Molecule is less liable to hydrolysis than are sulfates
N-Acyl taurines- good skin compatibility Exhibit a good stability over wide ranges of pH Compatible with hard water since their Mg and ca salts are
soluble
Monoalkyl phosphate-low skin irritation potential Used in face and body liquid cleansers
Acyl isethionate Used in soaps and shampoos for their mildness and foaming
properties
N-Acyl sarcocinate-produce a rich foam and have excellent skin compatibilities
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Cationic Surface Active Agents Has a positive charge Can be used as bactericidal agents Absorb onto negatively charged surfaces Are used as hair conditioners and fabric
softeners Are electrolytes and are incompatible with
anionic surface active agents Compatible with nonionics and zwitterionics Quaternary ammonium cmpds are among the
most extensively used cationic surface active agents
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Types of Cationic Surface Active Agents Alkylbenzyldimethyl Ammonium
Salt- germicide
Alkyl trimethyl Ammonium Salt-emulsifiers
-are also very effective germicides
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Nonionic Surface Active Agents Not electrolytes Has no charge Are not affected as much by the
presence of salts or charges in pH Hydrophilic group may contain
hydroxyl groups, polyoxyethylene groups, or saccharides
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Types of Nonionic Surface Active Agents Polyoxyethylene Alkyl Ether- are widely used in the
pharmaceutical and cosmetic industries The longer the polyoxyethylene chain, the more
hydrophilic the molecule and the higher the HLB value Fatty acid Alkanolamides- are used extensively in shampoos as
foam stabilizers and viscosity enhancers Sorbitan Fatty Acid Esters- are oil-soluble and form w/o
emulsions Are widely used in the combination with poloxyethylene
sorbital fatty acid esters Polyoxyethylene Sorbitan fatty Acid Esters [TWEEN]-hydrophilic
and form o/w emulsions Used extensively in the pharmaceutical, cosmetic, and
food industries Alkyl Polyglucoside-used in dishwashing detergents and
shampoos
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Zwitterion Surface Active Agents
Compatible with all types of surface active agents
Can be anionic, cationic or zwitterionic depending on the pH of the medium they are in
Main use is as cosurfactants to boost the foaming properties of other surfactants
N-alkylbetaines-lead to minimal skin irritation
-hard waters does not affect their foaming properties
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Insoluble Monolayers at Liquid Surfaces
Molecules which are not soluble in the bulk of liquids
A.k.a. Langmuir films
If the number of molecules on the surface of the water is low, the molecules will be far away from each other, trying to cover the whole surface
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Langmuir Film Balance
An instrument that can control the area of water surface available for the floating fatty acid molecules
movable barrier that moves tangiential to the water surface
Data are presented as plots of the surface pressure π as a function of the area A per molecule
Surface pressure-the horizontal force between the pure substrate, γ0, and the surface tension of the substate with the film on it.
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Langmuir Film Balance
• A Langmuir film balance facilitates the controlled preparation of model membranes at the air/water interface
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Walking on water Small insects such as the water strider can walk
on water because their weight is not enough to penetrate the surface.
Floating a needle If carefully placed on the surface, a small needle
can be made to float on the surface of water even though it is several times as dense as water. If the surface is agitated to break up the surface tension, then needle will quickly sink.
Don't touch the tent! Common tent materials are somewhat rainproof
in that the surface tension of water will bridge the pores in the finely woven material. But if you touch the tent material with your finger, you break the surface tension and the rain will drip through.
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Soaps and detergents help the cleaning of clothes by lowering the surface tension of
the water so that it more readily soaks into pores and soiled areas.
Clinical test for jaundice Normal urine has a surface tension of about 66 dynes/cm but if
bile is present (a test for jaundice), it drops to about 55. In the Hay test, powdered sulfur is sprinkled on the urine surface. It will float on normal urine, but sink if the S.T. is lowered by the bile.
Washing with cold water The major reason for using hot water for washing is that its
surface tension is lower and it is a better wetting agent. But if the detergent lowers the surface tension, the heating may be unneccessary.
Surface tension disinfectants Disinfectants are usually solutions of low surface tension. This
allow them to spread out on the cell walls of bacteria and disrupt them. One such disinfectant, S.T.37, has a name which points to its low surface tension compared to the 72 dynes/cm for water.