BITS Pilani

Pilani Campus

CHEM F312 : Physical Chemistry IV

Semester I: AY 2023-24
Lecture-37, 01 December 2023, Friday

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Review of the Last Lecture:

• Surfaces and nano-particles;

• Melting point and other thermodynamic property
changes as the particle size decreases and surface area
increases;
• Band theory;
• Introduction to interfacial and surface tensions;
𝒘𝒐𝒓𝒌 (𝒆𝒏𝒆𝒓𝒈𝒚) 𝑱
• 𝜸= = = 𝑵/𝒎
𝒂𝒓𝒆𝒂 𝒎𝟐

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 Surface Phenomena

Gibbs procedure for modifying thermodynamic

equations, by including interfacial tension.
Z

Left: P is the pressure in all directions in α and β phases.

However, in interphase region P is felt only in z direction and
not in x,y direction.
Right: Gibbs suggestion: Gibbs dividing surface – 0 volume
but non-zero thermodynamic properties.
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Surface Phenomena

Curved interface:

α phase is on the concave side of the surface.

Pα > Pβ.
If more of α is sent in then the volume of the α and
consequently the interface area increases. More
work is required. Therefore, Pα > Pβ.
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 Surface Phenomena

Greater force is required to push the lower piston

than to push the upper piston for the same volume.
If there is a membrane separation then the
membrane exerts pressure on α making Pα > Pβ.

Spherical Interface:
Piston is pushed inside –dV
(volume change) occurs.
Volume of interfacial region is neglected. BITS Pilani, Pilani Campus
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 Surface Phenomena

Combining with the previous result,

R – radius up to interface.
Sphere volume = 4/3 πR3
Sphere surface area = 4πR2
Ω is the solid angle in steradians; 4π steradians for
full sphere.
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Surface Phenomena

𝜶
𝛀 𝟒 𝛀
𝑽 = 𝝅𝑹𝟑 ; 𝓐= 𝟒𝝅𝑹𝟐
𝟒𝝅 𝟑 𝟒𝝅

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Surface Phenomena

R  ∞ (planar surface) Pα = Pβ
R  0 (Pα – Pβ) reaches maximum value.
Example: R = 1 cm  pressure difference 0.1 torr
R = .01 cm  pr. diff = 10 torr.

gas bubble pressure > bulk liquid

pressure.
gas at the concave side.

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 Surface Phenomena

Vapor pressure of a tiny droplet of a liquid > vapor

pressure of the same liquid in bulk.

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 Surface Phenomena

Capillary rise:
a) 0o ≤ θ < 90o
b) 90o < θ < 180o
Shape depends on the relative
adhesive forces and the internal cohesive forces of
the liquid.
a) Liquid on convex side
adhesive forces of glass – liquid > cohesive forces of
liquid – liquid.
b) Liquid on concave side
adhesive forces of glass – liquid < cohesive forces of
liquid – liquid.
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 Surface Phenomena
P1 = P 6 ; P2 = P5 ; P2 = P3
But P4 < P5 therefore
P4 < P3 ; unlike bulk liq.
P4 is not same as P3
P8 – P2 = P5 – P4 = (P5 – P7)
+(P7 – P4)
P2 – P8 = ραgh
(ρα = density of α)
P4 – P7 = ρβgh & P5 – P7 = 2γ/R
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 Surface Phenomena

a) At θ = 0 R = radius of the capillary = r.

b) For θ # 0 r = R cos θ  R = r/cos θ

For liquid mercury the value of θ = 140o and hence capillary

depression in stead of capillary rise happens.
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 Surface Phenomena

Colloids:
• Example: Let AgCl particles instead of
precipitating in H2O, get dispersed in the solution;
then we get a colloidal solution.
• Small tiny crystals being present in liquid
phase; the particles in the solution will be referred
as “Dispersed Phase” or “Colloidal Particles”;
• To qualify as a colloid, the particle dimension
should be 1-1000 nm only (at least in one
dimension);
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 Surface Phenomena

• In general, not only solids, but liquids and gases

can also be dispersed; In case of gases the molecules
will be individually moving;

• The medium in which the particles are

dispersed is known as “Dispersion Medium” or
“Continuous Phase” and again this can be
solid/liquid/gas;

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 Surface Phenomena

• “Sol” is the term used for colloidal systems

with dispersion medium as liquid /gas; For example,
in aerosol the dispersion medium is a gas;

• Real life examples:

“Fog” – aerosol with liquid particles;
“Smoke” – aerosol with liquid and solid
particles;

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