1. An insoluble monomolecular film forms when a slightly soluble material is spread on a liquid surface, such as water. The molecules stand vertically and pack closely, with thickness equaling molecular length.
2. Film pressure is measured as the difference between the surface tension of the clean liquid and the surface tension of the liquid covered by the film. The film resists contraction of the clean surface.
3. A π-A curve plots the relationship between film pressure and film area, showing phase changes as the film is compressed, from a gas-like to liquid-like to solid-like state.
SURFACE TENSION, INTERFACIAL TENSION, SURFACE FREE ENERGY, Measurement of surface and interfacial tension-capillary rise method, drop number method, drop weight method, Du Nuoy tensiometer method, Spreading of liquids, spreading coefficient, surface active agents, hydrophilic-lipophilic balance, soluble monolayers, Adsorption on solid surface, Isotherms
Surface and Interfacial tension [Part-3(a)](Measurement of Surface and Inter...Ms. Pooja Bhandare
MEASUREMENT OF SURFACE AND INTERFACIAL TENSION
Capillary Rise Method, Drop Count and Weight Method.
Wilhelmy Plate Methods ,The DuNouy Ring Method.
Capillary Rise Method: Upward force due to surface tension: Drop count and Weight method Downward Force: Drop weight method: Drop count method
SURFACE TENSION, INTERFACIAL TENSION, SURFACE FREE ENERGY, Measurement of surface and interfacial tension-capillary rise method, drop number method, drop weight method, Du Nuoy tensiometer method, Spreading of liquids, spreading coefficient, surface active agents, hydrophilic-lipophilic balance, soluble monolayers, Adsorption on solid surface, Isotherms
Surface and Interfacial tension [Part-3(a)](Measurement of Surface and Inter...Ms. Pooja Bhandare
MEASUREMENT OF SURFACE AND INTERFACIAL TENSION
Capillary Rise Method, Drop Count and Weight Method.
Wilhelmy Plate Methods ,The DuNouy Ring Method.
Capillary Rise Method: Upward force due to surface tension: Drop count and Weight method Downward Force: Drop weight method: Drop count method
When phases exist together, the boundary between two of them is known as interface.
When the phase is in contact with atmosphere it is termed as surface.
This presentation covers concepts such as surface tension, surface energy, liquid drops and bubbles, wetting, capillarity at the elementary school level. Comment down in a box for improvement.
Dispersion system
suspensions
interfacial properties of suspensions
zeta potential
Sedimentation parameters
Settling in suspension
Formulation of suspension
Preparation of suspension
In this presentation:
Surface Tension
Interfacial Tension
Definition of inerfacial tension in different ways
Measurement of interfacial and surface tesion
INCLUDES SPREADING COEFFICIENT AND ITS THEORY AND ALSO FEW OF ITS APPLICATION IN PHARMACEUTICAL FIELD
WILL BE HELPFUL FOR B PHARMACY STUDENTS
INCLUDES HOW IT IS DERIVED AND ALSO HOW IT IS RELATED TO SPREADING OF A CREAM OR OINTMENT ON OUR SKIN
IMPORTANCE OF SPREADING COEFFICIENT
Rheology is the science that study flow of fluids. Viscosity is the main parameter of flow. Newtonian & non newtonian are the two types of flow behavior according to newtons law of flow. non-newtonian flow can be plastic, pseudoplastic, dilatant, thixotropic, antithixotropic or rheopexy. viscosity can be determined by using various viscometers such as capillary viscometer, cup & bob viscometer, cone & plate viscometer, falling sphere viscometer, brookfield viscometer, etc. factors affeting viscosity are intrinsic, extrinsic or temperature dependence.
When phases exist together, the boundary between two of them is known as interface.
When the phase is in contact with atmosphere it is termed as surface.
This presentation covers concepts such as surface tension, surface energy, liquid drops and bubbles, wetting, capillarity at the elementary school level. Comment down in a box for improvement.
Dispersion system
suspensions
interfacial properties of suspensions
zeta potential
Sedimentation parameters
Settling in suspension
Formulation of suspension
Preparation of suspension
In this presentation:
Surface Tension
Interfacial Tension
Definition of inerfacial tension in different ways
Measurement of interfacial and surface tesion
INCLUDES SPREADING COEFFICIENT AND ITS THEORY AND ALSO FEW OF ITS APPLICATION IN PHARMACEUTICAL FIELD
WILL BE HELPFUL FOR B PHARMACY STUDENTS
INCLUDES HOW IT IS DERIVED AND ALSO HOW IT IS RELATED TO SPREADING OF A CREAM OR OINTMENT ON OUR SKIN
IMPORTANCE OF SPREADING COEFFICIENT
Rheology is the science that study flow of fluids. Viscosity is the main parameter of flow. Newtonian & non newtonian are the two types of flow behavior according to newtons law of flow. non-newtonian flow can be plastic, pseudoplastic, dilatant, thixotropic, antithixotropic or rheopexy. viscosity can be determined by using various viscometers such as capillary viscometer, cup & bob viscometer, cone & plate viscometer, falling sphere viscometer, brookfield viscometer, etc. factors affeting viscosity are intrinsic, extrinsic or temperature dependence.
FMM- UNIT I FLUID PROPERTIES AND FLOW CHARACTERISTICSKarthik R
Units and dimensions- Properties of fluids- mass density, specific weight, specific volume, specific gravity, viscosity, compressibility, vapor pressure, surface tension and capillarity. Flow characteristics – concept of control volume - application of continuity equation, energy equation and momentum equation.
Operation “Blue Star” is the only event in the history of Independent India where the state went into war with its own people. Even after about 40 years it is not clear if it was culmination of states anger over people of the region, a political game of power or start of dictatorial chapter in the democratic setup.
The people of Punjab felt alienated from main stream due to denial of their just demands during a long democratic struggle since independence. As it happen all over the word, it led to militant struggle with great loss of lives of military, police and civilian personnel. Killing of Indira Gandhi and massacre of innocent Sikhs in Delhi and other India cities was also associated with this movement.
2024.06.01 Introducing a competency framework for languag learning materials ...Sandy Millin
http://sandymillin.wordpress.com/iateflwebinar2024
Published classroom materials form the basis of syllabuses, drive teacher professional development, and have a potentially huge influence on learners, teachers and education systems. All teachers also create their own materials, whether a few sentences on a blackboard, a highly-structured fully-realised online course, or anything in between. Despite this, the knowledge and skills needed to create effective language learning materials are rarely part of teacher training, and are mostly learnt by trial and error.
Knowledge and skills frameworks, generally called competency frameworks, for ELT teachers, trainers and managers have existed for a few years now. However, until I created one for my MA dissertation, there wasn’t one drawing together what we need to know and do to be able to effectively produce language learning materials.
This webinar will introduce you to my framework, highlighting the key competencies I identified from my research. It will also show how anybody involved in language teaching (any language, not just English!), teacher training, managing schools or developing language learning materials can benefit from using the framework.
Biological screening of herbal drugs: Introduction and Need for
Phyto-Pharmacological Screening, New Strategies for evaluating
Natural Products, In vitro evaluation techniques for Antioxidants, Antimicrobial and Anticancer drugs. In vivo evaluation techniques
for Anti-inflammatory, Antiulcer, Anticancer, Wound healing, Antidiabetic, Hepatoprotective, Cardio protective, Diuretics and
Antifertility, Toxicity studies as per OECD guidelines
Normal Labour/ Stages of Labour/ Mechanism of LabourWasim Ak
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Exploiting Artificial Intelligence for Empowering Researchers and Faculty, In...Dr. Vinod Kumar Kanvaria
Exploiting Artificial Intelligence for Empowering Researchers and Faculty,
International FDP on Fundamentals of Research in Social Sciences
at Integral University, Lucknow, 06.06.2024
By Dr. Vinod Kumar Kanvaria
Acetabularia Information For Class 9 .docxvaibhavrinwa19
Acetabularia acetabulum is a single-celled green alga that in its vegetative state is morphologically differentiated into a basal rhizoid and an axially elongated stalk, which bears whorls of branching hairs. The single diploid nucleus resides in the rhizoid.
June 3, 2024 Anti-Semitism Letter Sent to MIT President Kornbluth and MIT Cor...Levi Shapiro
Letter from the Congress of the United States regarding Anti-Semitism sent June 3rd to MIT President Sally Kornbluth, MIT Corp Chair, Mark Gorenberg
Dear Dr. Kornbluth and Mr. Gorenberg,
The US House of Representatives is deeply concerned by ongoing and pervasive acts of antisemitic
harassment and intimidation at the Massachusetts Institute of Technology (MIT). Failing to act decisively to ensure a safe learning environment for all students would be a grave dereliction of your responsibilities as President of MIT and Chair of the MIT Corporation.
This Congress will not stand idly by and allow an environment hostile to Jewish students to persist. The House believes that your institution is in violation of Title VI of the Civil Rights Act, and the inability or
unwillingness to rectify this violation through action requires accountability.
Postsecondary education is a unique opportunity for students to learn and have their ideas and beliefs challenged. However, universities receiving hundreds of millions of federal funds annually have denied
students that opportunity and have been hijacked to become venues for the promotion of terrorism, antisemitic harassment and intimidation, unlawful encampments, and in some cases, assaults and riots.
The House of Representatives will not countenance the use of federal funds to indoctrinate students into hateful, antisemitic, anti-American supporters of terrorism. Investigations into campus antisemitism by the Committee on Education and the Workforce and the Committee on Ways and Means have been expanded into a Congress-wide probe across all relevant jurisdictions to address this national crisis. The undersigned Committees will conduct oversight into the use of federal funds at MIT and its learning environment under authorities granted to each Committee.
• The Committee on Education and the Workforce has been investigating your institution since December 7, 2023. The Committee has broad jurisdiction over postsecondary education, including its compliance with Title VI of the Civil Rights Act, campus safety concerns over disruptions to the learning environment, and the awarding of federal student aid under the Higher Education Act.
• The Committee on Oversight and Accountability is investigating the sources of funding and other support flowing to groups espousing pro-Hamas propaganda and engaged in antisemitic harassment and intimidation of students. The Committee on Oversight and Accountability is the principal oversight committee of the US House of Representatives and has broad authority to investigate “any matter” at “any time” under House Rule X.
• The Committee on Ways and Means has been investigating several universities since November 15, 2023, when the Committee held a hearing entitled From Ivory Towers to Dark Corners: Investigating the Nexus Between Antisemitism, Tax-Exempt Universities, and Terror Financing. The Committee followed the hearing with letters to those institutions on January 10, 202
2. Introduction
Interface: junction between boundary
Surface: One phase is gaseous
Liquid interface: liquid:gas,liquid:liquid
Solid interface: soild:gas, Solid:liquid
3.
4.
5.
6.
7.
8. Value of Surface tension indicate the nature of
intermolecular forces
Molecule in Mercury are held together by strong
mettalic bonds so high value of surface tension
9. Adhesion and Cohesion forces
Adhesion forces:
Forces which act between
molecules of different phase
cohesional forces are those
which act between molecules of
same phase
Cohesion forces:
Cohesion forces tend to keep
the phases separate while
adhesional forces tend to
increase the affinity of two
phases
If adhesional forces are stronger,
10.
11.
12. Providing min area at liquid and number of molecules
at the surface also minimizes
Liquid drops in air become spherical in shape because
a sphere has minimum surface area compared to
13.
14. Expression of surface tension
Surface tension
In term of force per unit length
Then force acting along the surface of liquid at
right angle to any line 1 cm in length
Dyne/cm
15. Effect of temp on surface tension
As per kinetic
theory,
Kinetic energy of
molecules is
proportional to the
absolute temp
Increase in temp:
energy of molecule
increase: decrease
in intermolecular
forces of attraction:
20. Surface energy and surface tension are two
interconnected concepts. The molecules on the
surface of a liquid are packed due to unbalanced
intermolecular forces than the molecules at the
center. This means there is a high energy density
at the surface of a liquid.
Surface energy can be defined as the energy
difference between the bulk of the material and
the surface of the material.
21.
22.
23.
24.
25.
26.
27.
28.
29. dW be the
work (surface
free energy)
needed to
displace the
movable bar
by a small
distance dS.
30.
31. =
- Sign indicates that
there is decrease in
the surface free
energy
"why is the pressure inside a soap bubble higher than
outside," is that a higher pressure than the local atmosphere is
required to make the bubble in the first place! This requirement
comes from the need to counterbalance the surface tension force.
44. Name of apparatus: Stalagnometer
Principle: Weight (W) of liquid falling from a capillary
is app. Proportional to the surface tension of liquid
Lower surface tension of liquid: smaller size of drops
formed
More no. of drops formed from same volume to the
liquid
2. Drop Formation
Method
48. Drop Weight method:
A
B
Drop Weight method:
Method 1:
Stalagmometer clamped vertically
Liquid sucked upto mark A
Liquid allowed to drop slowly till point B
20 to 30 drops collected
Weight of one drop is calculated
Surface tension determine by
γ=w/2πr
49. 2. Drop Formation Method
Drop Weight method:
Method 2:
About 2o droops of given liquid are received
from the drop pipette in a weighing bottle
Weight of one drop is calculated
Pipette clean & dried
Filled with second reference liquid (water)
Weight of one drop of reference liquid
calculated
W1=2πrγ1
W2=2πrγ2
γ1/ γ2 = W1/W2
Relative Surface tension of liquid = W1/W2
A
B
50. Relative Surface tension of liquid= Surface tension of liquid/Surface tension of water
= d1/d2 * n2/n1
, V=Volume, n= number of drops
v d
g
51.
52. WL= Reading on the balance prior to detachment, W is the weight of the
plate in air
L=Length
T= Thick
WL-W
WL-W
58. (Du Noüy Ring Tensiometer)
Detachment force is equal to the surface tension
multiple by the perimeter of the liquid detached
P=W= 2π (r1 +r2) γ
γ=P/ 2π (r1 +r2)
P= pull exerted through the torsion wire on the
ring and is read on the scale
W=force in term of weight
r1 & r2 = inner and outer radii of disc
59. Du Noüy Ring Tensiometer
A correction factor (β):
Variables: Radius of ring, Radius of wire, shape of liquid
supported by ring during detachment
γ=P/ 2π (r1 +r2) * β
γ= Dial reading in dynes
2*ring circumference
If radius of wire is small r1=r2
γ=P/ 4π r * β
Interfacial tension, ring is detached from the interface
between two immiscible liqid
* Correction factor
60.
61. 4. Spreading
Small quantity of an
immiscible liquid placed on
surface of another liquid
Spread as film on
surface of another
liquid
As Drop
Depends
upon
achievement
of a state of
min free
energy
62. 4. Spreading
Work of adhesion > work of cohesion
Spreading
Sate of minimum free energy
+ve or Zero
64. Because of more of cohesive force rather than
adhesive force between them
65.
66.
67.
68.
69. Presence of polar group
Benzene spreads on water not because of its polar nature but
because its cohesive force are much weaker than the adhesive
force
89. Not suitable for inter use (Unpleasant taste and irritant action on
intestinal mucosa)
(Inactive part)
90. Anionic
Surfactant
Alkali Soaps
Ammonium,
potassium and
sodium salts of
long chain fatty
acids such as
oleic, stearic and
ricinoleic acid
Unstable below pH
10
Incompatible with
acids
andpolyvalent
inorganic
Amine Soaps
Insitu by
reaction
between
amines e.g
Ethanolamin
e,
diethanolami
ne,
triethanolami
ne or
isopropanola
mine and
fatty acids
(Oleic acid)
Alkyl
sulphate and
phosphates
Ester formed
by reaction
of fatty
alcohol with
sulphuric
acid and
phosphoric
acid
respectively
Sodium
lauryl
sulphate,
sodium
cetostearyl
sulphate &
triethanolami
ne lauryl
Alkyl
sulphates
Disodium
sulfosuccinat
e
Wetting
agents
93. Cationic Surfactants
Cationic surfactant: Benzalkonium chloride and
benzethonium chloride
More popular as antiseptics or disinfecting agents
Secondary emulsifying agents for external application
Incompatible with anionic surfactants
Unstable at high pH
94.
95. Ionic characteristics depends the pH of system Below a certain
pH, cationic while above a defined pH, anionic . At intermediate
pH behave as zwitterions
106. Saponification number. : a
measure of the total free and
combined acids especially in a fat,
wax, or resin
acid value (or neutralization number or acid number or acidity) is themass of
potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of
135. Micellar Solubilization
An important property of micelles that has
particular significance in pharmacy is their
ability to increase the solubility of sparingly
soluble substances in water.
solubilization can be defined as the
spontaneous dissolving of a substance by
reversible interaction with the micelles of a
surfactant in water to form a
thermodynamically stable isotropic solution
with reduced thermodynamic activity of the
solubilized material
136. Micellar Solubilization
If we plot the solubility of a
poorly soluble compound
as a function of the
concentration of
surfactant,
The solubility is very low
until the surfactant
concentration reaches the
cmc.
At surfactant
concentrations above the
cmc the solubility
increases linearly with the
concentration of
137. Accordingly, (1)hydrophilic drugs can be adsorbed on
the surface of the micelle
(2) drugs with intermediate solubility should be
located in intermediate positions within the micelle such
as between the hydrophilic head groups of PEO
micelles (2) and in the palisade layer between the
hydrophilic groups and the first few carbon atoms of the
hydrophobic group, that is the outer core (3), and
completely insoluble hydrophobic drugs may be located
in the inner core of the micelle (4). The existence of
different sites of solubilization in the micelle results
from the fact that the physical properties, such as
microviscosity, polarity and hydration degree, are not
uniform along the micelle
138. Micellar Solubilization
Two state model of solubilization:
Dissolved fraction: less polar state involved the
hydrocarbon core
Adsorbed fraction: micelle water interface, environment is
more polar
Solubilising power of micelle: Adsorbed fraction+
Dissolved fraction
142. Kraft and cloud point
In the case of ionic surfactants, it is often observed that
the solubility undergoes a sharp, discontinuous increase
at some characteristic temperature, named the Krafft
temperature (TK)
Below the Krafft temperature solubility of the surfactant
is determined by the solid state properties, while above
it the surfactant solubility increases due to formation of
micelles, which are thermodynamically favored form .
The Kraft temperature varies with alkyl chain length and
structure, as well as with counterion.
143. Kraft and cloud point
Lowering of the Krafft temperature can be achieved by
introducing chain branching, multiple bonds in the alkyl
chain or bulkier hydrophilic groups in the surfactant
molecules. In this way intermolecular reactions that
promote crystallization are reduced
The Krafft temperature is usually determined either by
measuring the change of electrical conductivity with
temperature or visually observing the change of turbidity
of supersaturated surfactant solution (usually 1 wt %)
144. Kraft and cloud point
Knowledge of the Krafft temperature is crucial in
many applications since below TK the surfactant will
clearly not perform efficiently; hence typical
characteristics such as maximum surface tension
lowering and micelle formation cannot be achieved.
145. Cloud point
Nonionic surfactants containing oxyethylene groups are
very much affected by the temperature. While heating a
nonionic surfactant solution, it becomes turbid at a
specific temperature range.
The solution becomes “cloudy”. The temperature range
is called the cloud point, or cloud temperature.
146. Cloud point
Clouding is really a phase separation into two
micellous solutions; one with a high concentration of
surfactants, and one with a low concentration of
surfactants.
147. Cloud point
Produces a difference in density of micelle-rich and
micellar poor phases.
Larger particle: more visibly turbid: more light
scattering
The cloud point depends very much on the
polyoxyethylene chain length of the surfactant, a
longer chain corresponds to a higher cloud point
148. Types of monolayer at interfaces
1. Insoluble monomolecular layer or film
2.Soluble monomolecular layer or film
3.Mixed Film
149. Surface Film
Surfactant get adsirbed at surface of a liquid such as water
can be divided into two groups.
If the substance that forms the monolayer is insoluble in the
liquid subphase, the monolayer is called Langmuir layer
(e.g., a monolayer of stearic acid at air water interface).
On the other hand, if the substance is soluble in the bulk
phase, the monolayer is termed Gibbs layer (e.g., a
monolayer of sodium dodecyl sulfate at air water interface).
150. Parameters
1. Surface tension (γ)
2.Surface excess (Γ): The amount of
amphiphiles per unit area of surface in excess
of that in the bulk of the liquid
3. Conc of the amphiphiles in the bulk of liquid
151. 1. Insoluble monomolecular layer or
film
Small amount of certain slightly soluble materials
are placed on a clean surface of water, they
spread to form a layer one molecule in thickness
Thickness of film can be determine if area of film
and volume of spreading liquid is known
The film thickness is equal to the length of the
molecules standing in a vertical position on the
surface when the molecules are packed in closest
arrangement
Apparatus: Film balance
152. Surfactant is dissolved in a volatile
solvent (Hexane)
Solution is then placed on the surface
of the substrate (water)
Solution spread as film on surface
Solvent evaporates
Leaving molecules of surfactant on the
surface
1. Insoluble monomolecular layer or
film
156. Insoluble Monomolecular layers or
film
Film pressure is difference between the
surface tension (γ0) of substrate (water) and
surface tension (γ) of the film covered surface
Π =(γ0- γ)
Film pressure, π, is an expansion pressure
exerted on the monolayer that opposes the
surface tension, γ0, or contraction of the clean
(water) surface. The surface active molecules
of the monolayer are thought to insert
themselves into the surface of the water
molecules of a film balance to reduce the
157. Insoluble Monomolecular layers or film
The presence of the surfactant molecules
increases the ease of expansion, presumably
by breaking or interfering with hydrogen
bonding, van der Waals interaction, and other
cohesive forces among the water molecules.
These attractive forces produce the ―springl
ike action in the water surface, as measured
by the surface tension, γ0, and the
introduction of surfactant molecules into
the clean water surface reduces the
springiness of the interacting water
158. Insoluble Monomolecular layers or
film
The compressive force per unit area on the float is
known as the surface or film pressure
Area of the film and film pressure p at each position are
measured
A graph of Area of the film (A) against film pressure π
π-A curve
159. a variety of phase changes
are observed when an
insoluble film is spread at an
interface and then
compressed.
straight-chain saturated
aliphatic compound at the air–
water interface.
When the film is spread over
an area greater than 50 to 60
Å2/molecule (region G), it
exerts little pressure on the
floating barrier. The film acts
like a gas in two dimensions.
As the film begins to be
compressed (region L1 - G), a
liquid phase, L1, appears that
coexists in equilibrium with
160. The liquid expanded state
(region L1) can be
thought of as a bulk liquid
state.
Further compression of the
film often leads to the
appearance of an
intermediate phase (region
I) and then a less
compressible condensed
liquid state, region L2.
This then gives way to the
least compressible state,
region S, where the film can
be regarded as being in a
two-dimensional solid state.
In these latter stages of film
compression, the film or
161. This increase in π with
compression of the
surfactant film results from
surface-active molecules
being forcibly inserted and
crowded into the surface.
This process opposes the
natural tendency of the
water surface to contract,
and the surface tension
decreases from γ0 to γ.
Finally, the molecules slip
over one another, and the
film breaks when it is greatly
compressed.
162. Insoluble monolayers. Insoluble monolayer films exhibit
characteristics that can be equated to those of the solid, liquid,
and gaseous states of matter.
(a) Gaseous film. Molecules are apart and have significant
surface mobility. The molecules essentially act independently.
(b) Liquid film. Monolayer is coherent and relatively densely
packed but is still compressible.
(c) Condensed film. Monolayer is coherent, rigid, essentially
incompressible, and densely packed, with high surface
viscosity. The molecules have little mobility and are oriented
163.
164. Soluble monomolecular layer or film
Certain materials amyl alcohol
Form soluble monomolecular layer or film on
surface of water on adding directly to water
Monolayer formed
Film compression
No increase in film pressure π
165. Soluble monomolecular layer or film
Polar molecules from monomolecular film when
placed on water
On compression: molecules enter the aqueous
bulk solution rather than to remain as an intact
insoluble film
Constant surface pressure even with increased
compression
Constant number of molecules per unit area that
remains at the surface at equilibrium with
dissolved molecules
This behaviour is greater for substances
exhibiting weaker intermolecular interaction and
166. Soluble monomolecular layer or film
Gibbs equation which relates surface
concentration to surface tension change
produced at different surface activities
Γ: Surface concentration (excess surfactant found per unit area at the
surface with respect to the amount found in the bulk of the liquid)
C: Conc. of surfactant in bulk of liquid
T: absolute temp
Dϒ/dc: change in surface tension with change in bulk conc. of the
surfactant
167. Mixed Film
If two different SAA mixed
Allowed to spread on the surface of liquid
Form a mixed monomolecular film
Water soluble surfactant can penetrate into an
insoluble monolayer of surfactant
Molecular association between two surfactant due
to strong attraction between polar groups
168.
169.
170.
171. Adsorption at solid interface
Adsorption of material at solid
interfaces can take place from either
an adjacent liquid or gas phase.
Diverse applications as the removal of
objectionable odors from rooms and
food
The principles of solid–liquid adsorption
are used in decolorizing solutions,
adsorption chromatography,
detergency, and wetting.
similar to that discussed for liquid
surfaces.
Thus, adsorption of this type can be
considered as an attempt to reduce
the surface free energy of the solid.
172. Adsorption at solid interface
The surface tensions of solids are invariably more
difficult to obtain, however, than those of liquids.
In addition, the solid interface is immobile in comparison
to the turbulent liquid interface.
The average lifetime of a molecule at the water–gas
interface is about 1 μ sec, whereas an atom in the
surface of a nonvolatile metallic solid may have an
average lifetime of 1037 sec.
Frequently, the surface of a solid may not be
homogeneous, in contrast to liquid interfaces.
173. Adsorption at solid interface
Adsorption
at
Solid/Gas
interface
Adsorption
at
solid/liquid
interface
Adsorption
at solid
interface
174.
175. The Solid–Gas Interface
The degree of adsorption of a gas by a solid
depends
1.Chemical nature of the adsorbent (the material used
to adsorb the gas) and
2.Adsorbate (the substance being adsorbed),
3. The surface area of Adsorbent,
4. Temperature,
5.Partial pressure of the adsorbed gas.
176. Reversible, the removal of the adsorbate from the adsorbent being known as
desorption
Desorption by increasing the temperature and reducing the pressure
Primary chemical bonds, is irreversible unless the bonds are broken.
177.
178.
179. The Solid–Gas Interface
The relationship between the amount of gas
physically adsorbed on a solid and the equilibrium
pressure or concentration at constant temperature
yields an adsorption isotherm
The term isotherm refers to a plot at constant
temperature
The number of moles, grams, or milliliters, x, of gas
adsorbed on, m, grams of adsorbent at standard
temperature and pressure is plotted on the vertical
axis against the equilibrium pressure of the gas in mm
Hg on the horizontal axis.
180. The Solid–Gas Interface
First systemic attempt to classify the adsorption
isotherms for gas-solid by BDDT in 1940 into 5 types
Addition 1 by Sing
IUPAC classification :
181. It consists essentially of a balance
contained within a vacuum
system.
The solid, previously degassed, is
placed on the pan, and known
amounts of gas are allowed to
enter.
The increase in weight at the
corresponding equilibrium gas
pressures is recorded. This can
be achieved by noting the
extension of a calibrated quartz
spring used to suspend the pan
containing the sample.
The data are then used to
182.
183. Type 1 isotherm
Microporous structure
Micropore filling occurs at relatively
low pressures
Rapid rise in adsorption with
increasing pressure followed by
leaving off due to adsorption being
restricted to monolayer
Chemisorption types: all chemical
groups available get saturated very
rapidly
Adsorption of nitrogen on carbon at
77°K
184. Type II isotherm
Sigmoidal
Physical adsorption of gases onto
non-porous solid
Point B – the beginning of the middle
almost linear section – usually
corresponds to the completion of
monolayer coverage.
A more gradual curvature is an
indication of a significant amount of
overlap of monolayer coverage and
the onset of multilayer adsorption.
B
185. Type III isotherm
There is no Point B and therefore
no identifiable monolayer formation;
The adsorbent-adsorbate
interactions are now relatively weak
Low adsorption at low relative
pressures
Adsorbed molecules are clustered
around the most favorable sites on
the surface of a nonporous or
macroporous solid.
Adsorption of water molecules on
carbon where primary adsorption
site are oxygen based
188. Type VI isotherm
The reversible stepwise
Is representative of layer-by-layer adsorption on a
highly uniform nonporous surface.
The step-height now represents the capacity for each
adsorbed layer, while the sharpness of the step is
dependent on the system and the temperature.
Amongst the best examples of Type VI isotherms are
those obtained with argon or krypton at low
temperature on graphitised carbon blacks.
189.
190.
191. Langmuir theory and adsorption
isotherm
Langmuir published a new model isotherm for gases
adsorbed onto solids, which retained his name.
The Langmuir adsorption model is the most common
one used to quantify the amount of adsorbate
adsorbed on an adsorbent as a function of partial
pressure at a given temperature.
194. Langmuir theory and adsorption
isotherm
The rate of adsorption was related to the number of
unoccupied sites available at any instant
The rate of desorption of adsorbed molecules was
related to the number of occupied sites onto which
the gas was already adsorbed
195.
196. Let θ be the fraction of sites occupied by gas molecules at pressure p. Then the
fraction of sites unoccupied is 1-θ
The rate (r1) of adsorption of gas molecules on the surface of adsorbent is
proportional to the unoccupied sites and pressure i.e
r1∝ (1-θ)p
r1=K1(1-θ)p
The rate (r2) of desorption (or evaporation) of adsorbed molecules on the surface
is proportional to the fraction of site occupied
i.e. r2 ∝ θ
r2+=K2 θ
At equilibrium, the rate of adsorption (r1) is equal to the rate of desorption (r2)i.e
K2 θ=K1(1- θ)p
K2 θ=K1p-K1θp
K2 θ+K1θp =K1p
θ(K2+K1p)=K1p
θ= K1p/(K2+K1p)
197. Dividing by K2
θ= (K1/K2)p/{K2/K2+(K1/K2)p}
θ= (K1/K2)p/{1+(K1/K2)p}
Replacing K1/K2 by a constant b & ө by y/ym, the equation is given
as
y/ym=bp/1+bp
Ө: fraction of centres occupied & it can be replaced by y/ym,
y/ym: mass of gas adsorbed per gram of adsorbent at pressure p &
constant temp
Ym: mass of gas necessary to form a monolayer per gram of
adsorbent
Y=ymbp/1+bp
198. Langmuir theory and adsorption
isotherm
For convenience of plotting the pxperimental data,
Langmuir equation may be obtained in its linear from by
inverting the equation and multiplying by p
1/y=1+bp/ymbp
p/y=p(1+bp/ymbp)
p/y=P+bp2/ymbp
p/y=(p/ymbp)+(bp2/ymbp)
p/y=(1/ymb) + (p/ym)
p/y Vs p: straight line
p/y against p should yield a straight line,
199. BET Equation
Langmuir & Freundlich described only type 1
adsorption isotherm. In this case, at low pressure
the amount of gas adsorbed is proportional to the
pressure and at higher pressures the adsorption
became less and level off to a constant value
indicating that all the available sites have been filled
up. At this stage adsorption is independent of
pressure.
Type II isotherms are sigmoidal in shape and occur
when gases undergo physical adsorption onto
nonporous solids to form a monolayer followed by
multilayer formation. The first inflection point
represents the formation of a monolayer; the
continued adsorption with increasing pressure
200. BET Equation
Type II isotherms are best described by an expression
derived by Brunauer, Emmett, and Teller and termed for
convenience the BET equation.
In this case, it is assumed that the molecular were adsorbed
on to fixed sites and there was no lateral interaction between
molecules and that the heat of formation of monolayer is
equal to heat of condensation
201. BET Equation
where p is the pressure of the adsorbate molecule in mm Hg
at which the mass,
y, mass vapor per gram of adsorbent is adsorbed,
p0 is the saturated vapor pressure i.e. when the adsorbent is
saturated with adsorbate vapor,
Ym is the mass quantity of vapor adsorbed per unit mass of
adsorbent when the surface is covered with a monomolecular layer,
and
b is a constant proportional to the difference between the heat of
adsorption of the gas in the first layer and the latent heat of
condensation of successive layers.
.
202. Adsorption at Solid-Liquid
interface
Drugs such as dyes, alkaloids, fatty acids, and even
inorganic acids and bases can be absorbed from
solution onto solids such as charcoal and alumina
Thus adsorption on solid is function of the relative
adsorption of solute and solvent
At low concentration of solution: adsorption of solute
molecule onto solid similar to that of gas
Langmuir adsorption isotherm equation with slight
modification,
203. where c is the equilibrium concentration in
milligrams of alkaloidal base per 100 mL of
solution,
y : x/m is the mass of solute (x) per gram of
adsorbent m at equilibrium
x, in milligrams adsorbed per gram,
m, of clay (i.e., y = x/m), and
B: adsorption coefficient
Ym: adsorptive capacity of the solid i.e gram of
solute per gram of adsorbent when fully covered
(i.e mono-molecular later)
209. Detergency
Good wetting property
Reduced adhesion between dirt & solid
Once removed, surfactant gets adsorbed on particles
surface: Charge & hydrating barriers: prevent
deposition of dirt
If dirt is oily: either emulsify or solubilized
210. Electrical properties of interfaces
The Electric Double Layer
The electric double layer at the surface of
separation between two phases,
showing distribution of ions. The system as a whole is
electrically neutral.
211. The Electric Double Layer
Consider a solid surface in
contact with a polar solution
containing ions, for example,
an aqueous solution of an
electrolyte. Furthermore, let
us suppose that some of the
cations are adsorbed onto the
surface, giving it a positive
charge.
Remaining in solution are the
rest of the cations plus the
total number of anions added.
These anions are attracted to
the positively charged surface
by electric forces that also
serve to repel the approach of
212. The Electric Double Layer
In addition to these electric
forces, thermal motion tends
to produce an equal
distribution of all the ions in
solution.
As a result, an equilibrium
situation is set up in which
some of the excess anions
approach the surface,
whereas the remainder are
distributed in decreasing
amounts as one proceeds
away from the charged
surface.
At a particular distance from
the surface, the
213. The Electric Double Layer
It is important to remember
that the system as a whole is
electrically neutral, even
though there are regions of
unequal distribution of anions
and cations.
aa′ is the surface of the solid.
The adsorbed ions that give
the surface its positive
charge are referred to as the
potential-determining ions.
Immediately adjacent to this
surface layer is a region of
tightly bound solvent
molecules, together with
some negative ions, also
214. The Electric Double Layer
These ions, having a charge
opposite to that of the potential-
determining ions, are known as
counterions or gegenions. The
degree of attraction of the
solvent molecules and
counterions is such that if the
surface is moved relative to the
liquid, the shear plane is bb′
rather than aa′, the true surface.
In the region bounded by the
lines bb′ and cc′, there is an
excess of negative ions. The
potential at bb′ is still positive
because, as previously
mentioned, there are fewer
215. 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 in
potential between the actual
surface and the
electroneutral region of the
solution.
The potential located at the
shear plane bb′ is known as
the electrokinetic, or zeta,
potential, δ. The zeta
potential is defined as the
difference in potential
216. Nernst and Zeta Potentials
The potential initially
drops off rapidly,
followed by a more
gradual decrease as
the distance from the
surface increases.
This is because the
counterions close to
the surface act as a
screen that reduces
the electrostatic
attraction between the
charged surface and
217. Nernst and Zeta Potentials
The zeta potential has practical
application in the stability of
systems containing dispersed
particles because this potential,
rather than the Nernst potential,
governs the degree of repulsion
between adjacent, similarly
charged, dispersed particles.
If the zeta potential is reduced
below certain value (which
depends on the particular system
being used), the attractive forces
exceed the repulsive forces, and
the particles come together. This
phenomenon is known as
flocculation and is discussed in