BITS Pilani

Pilani Campus

CHEM F312 : Physical Chemistry IV

Semester I: AY 2023-24
Lecture-38, 04 December 2023, Monday

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Review of the Last Lecture:

• Gibbs dividing surface - a concept to define interface;

• Curved interfaces and pressure differences between
phases;
• Consequences in pressure of Gas bubbles; vapour
pressure of droplets;
• Capillary rise; adhesive and cohesive forces;

• Introduction to colloids.

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 Surface Phenomena
• Emulsions: Sol where both dispersed phase and dispersion
medium are liquids; Example: oil in liquid;
• Colloidal Suspension: Sol where dispersed phase is solid
and dispersion medium is a liquid;
• Foam: Gas bubbles are dispersed in liquid or solid
medium; 1000 nm limit is exceeded in these cases for the
size of bubbles; but the distance between the bubbles is less
than 1000 nm and hence classified as colloidal system; Here
the dispersion medium is in colloidal state.
• Example: Soap foams etc. in liquid + air; Porous rocks/
stones, pumice stones etc. - gas dispersed in solids (this
happens in volcanic conditions).
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Surface Phenomena

Two categories of dispersions:

(i) mono molecular particles dispersed: e.g.,
proteins in water; no scattering etc. are possible; no
interfacial area; the molecules may be solvated;
However, in case of large size polymers scattering
may be possible;
(ii) poly molecular particles dispersed: e.g.,
AgCl, Ag2S3, Au in water; small size of the particles
give large interfacial area.

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Surface Phenomena

Lyophilic colloids: Lyophilic = Solvent loving;

• e.g. proteins in water;
• spontaneous dispersion of dry (bulk) material in a
liquid;
• thermodynamically more stable than the two
phase system of dispersion medium and the bulk
colloid material;

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Surface Phenomena

• Soap in Water:

• Soap molecules have a polar head and a non-

polar tail; the non-polar tails aggregate (come
together) to create a hydrophobic core; The polar
heads are hydrophilic; BITS Pilani, Pilani Campus
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 Surface Phenomena

• This is called a micelle and the micelle formation

happens above a concentration value known as
critical micelle concentration (cmc);
• Above the cmc properties of the system change
sharply; Light scattering experiments show
micelles in size are from 20 nm to a few hundred
nm and spherical in shape.

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 Surface Phenomena

• This formation is reversible; on dilution the soap

particles are separated again as in a normal
solution; i.e., the micelle goes back to monomer
particles.
• Also at very high concentration the shape may be
non-spherical.
• Consider this as a single phase equilibrium with
nL ⇌ Ln.

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Surface Phenomena

Here the y-axis

corresponds to individual
concentrations Ci = [L] or
[Ln] and the x-axis
corresponds to total
stoichiometric
concentration written as
[L] + n [Ln]; The position of
change of slopes in both
curves correspond to cmc;
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 Surface Phenomena

• nL ⇌ nLn. The limit n∞ corresponds to a change

to two phase system;
• Micelles are formed naturally during many
biological activities; fat digestion with the help of
bile acids is one example.

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Surface Phenomena

Lyophobic (solvent hating) colloids:

• Example: AgCl solid in water;
• Formation is non-spontaneous; the colloid
formed is thermodynamically unstable compared to
the starting materials;
• However, can be stabilized in the dispersion
medium and the long life of such colloids is due to
the repulsion between particles arising after the
adsorption of ions of specific charges on the
surfaces;
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 Surface Phenomena

Lyophobic colloids:
• Can also be stabilized by coating techniques such
as polymer/ protein (gelatin) coating over the
surface of the particles.
There are some other methods of producing
lyophobic colloids;
• (i) precipitate the lyophobic substance in a very
dilute or very concentrated solution;
• (ii) mechanical breaking of particles and
dispersing it in liquids.
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Surface Phenomena

Sedimentation:
• Particles of non – colloidal suspensions slowly
settle down due to gravity;
• The sedimentation is possible in cases of particles
of bigger size in a sol;
• Based on sedimentation rates one can compare
the mass and size of the particles;
• Medical: Erythrocyte Sedimentation Rate (ESR –in
medical tests); Red blood cells settling rate
indicates inflammation etc.
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 Surface Phenomena

• Emulsions are of two types: oil in water or

water in oil; In both cases we have hydrophobic
interactions; Therefore, we require an emulsifying
agent to reduce the interfacial tension.
• Example: Milk (butter droplets (fat –oil) in
water); the emulsifying agent is Caesin – the protein
in the milk.

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Surface Phenomena

• Gel: Semi-rigid colloidal system; two

components and both the components are present
continuously in the system;
• Inorganic Gel : H2O trapped in tiny inorganic
crystals; Does not dissolve in water; Al(OH)3
gelatinous precipitate;
• Gelatin protein if cooled produces a polymer
gel; Entangled polymers – held by van der Waals
forces, H-bonds, and some covalent bonds make it
stable;
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 Surface Phenomena

• Aerogel: Evaporate the liquid component from the gel.

A strong – low density solid is produced; Air/gases replace
the liquid space.
• Si(OC2H5)4(l) + 2H2OSiO2(s) + 4C2H5OH (medium is
ethanol – solvent)
• In the above reaction tetraethyl-orthosilicate is
hydrolyzed in solution phase; Slowly the Si-O-Si network
develops in all directions making it amorphous solid at the
end. During the formation SiO2 will be a in a gel state
trapping solvent molecules; As the solvent water and
ethanol are evaporated, silica gel or silica glass is formed.
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 Surface Phenomena

• Aerogel:
• Density: 0.1 – 0.003 g/cm3;
• pore diameter: 20 nm; surface area 800 m2/g ;
• free volume: 95 – 99.9 %;
• thermal conductivity:0.00015 J s-1 cm-1 K-1 (which is
extremely low for a solid).

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Physical Kinetics

Physical Kinetics:
• Irreversible, non-equilibrium;
• Energy and mass transfer between one part of the
system to other part OR between system and
surroundings;
• Temperature difference between the system and
surroundings  Thermal conduction;
• Force difference between the system and
surroundings  no mechanical equilibrium (Fluid
dynamics  viscosity etc.)
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 Physical Kinetics

• Concentration (chemical potential) difference

between the system and surroundings  matter
flow (diffusion etc.);
• Applied electrical forces  Electrical conduction
(ionic, electronic movements, energy transfer
etc.).
• Therefore, Rate of transport is proportional to the
Gradient (spatial derivative) of some physical
property.

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 Physical Kinetics

Now let us focus our attention on one property of

Fluid, viz., Viscosity.
• Consider pressure gradient in fluids.
• The fluid’s resistance to flow = η (viscosity – a
property of the fluid)
• The figure below shows fluid flow between two
plates;

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 Physical Kinetics

 vy is maximum at the mid-point between plates;

 vy is minimum near the plate almost equals to zero
called “no slip condition”;
 This zero flow happens very near to the solid
surface, where fluid molecules are attracted to the
rough surfaces of the solid (adhesive forces);
 vy is a function of x;
 Adjacent layers move with different speeds;
 Adjacent layers while slipping exert a force on the
other layer (viscosity);
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 Physical Kinetics

 Consider an imaginary surface of area 𝓐;

 Fluid in rest / motion force on the other layer at x
direction is P 𝓐;
 Because of speed differences, we get frictional
forces on the other layer as one layer slips;
 Fy = Frictional force on the fluid in y direction;
Fy α 𝓐
Fy α dvy /dx
𝒅𝒗𝒚
Fy = -η 𝓐
𝒅𝒙

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 Physical Kinetics

 Viscosity is the proportionality constant;

sometimes called as “dynamic viscosity”;
 -ve sign  the viscous force on the faster moving
layer is in the opposite direction of its motion;
 Force in y direction Fy is exerted by the faster
moving layer on the slower moving layer.
 By Newton’s third law, a force of –Fy will be
exerted by the slower moving layer on the faster
moving layer;

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 Physical Kinetics
 Thus viscous forces slow down the faster moving
layer and speeds up the slower moving layer;
 The above equation is Newton’s law of viscosity;
 This flow is called “laminar flow” or “streamlined
flow”; the flow rate should not be very high for
laminar flow;
 At high rates of flow, “Turbulent flow” happens
and does not exactly follow the above law;
 Laminar and turbulent flows are bulk flows;
 Very low pressures lead to molecular flow where
molecules move independently;
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 Physical Kinetics

 Turbulent flows can be controlled by adding long-

chain polymer molecules which reduces the resistance
to flow (This technique is followed in petroleum
industry often);
 Blood flow in normally laminar; turbulent blood flow
is indicative of ‘plaque’ formation;
 To make the blood flow laminar, or to control the
blood flow some therapies use the idea of introducing
non-toxic poly(ethylene oxide) in the blood flow.

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Physical Kinetics

For further materials which are covered in

class the slides could not be made in time; See
the accompanying hand written notes. Read
with the help of corresponding pages in the
Text Book.

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Molecular Interactions

Good Luck

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