Liquid-Solid Interfaces: Wetting and Spreading

Polar and non-polar aspects and contributions to wetting

Behavior of different chemical systems

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 Semi-Empirical Models: GOOD-GIRIFLCO-FOWKES-YOUNG Model
Good-Girifalco approach for intermolecular energy of interaction for liquid –liquid interfaces
(on films of liquid substrates)
We saw earlier that WAB = 2φ(σAσB)1/2 based on the “Geometric mean Rule” for intermolecular energy εAB
If it is assumed that the two phases are mutually entirely miscible and interact only through additive
dispersion forces (van der Waals type) whose constants obey a “Geometric mean rule/law”
C1,AB = (C1,AA C 1,BB) where C are the constants in the Kirkwood-Muller form of the general form given by
ε(x) = − C1x-6 – C2x-8 – C3x-10 + ….
Then the interfacial free energies should obey the equation
σAB = σA + σB − 2φ (σA σB)1/2 φ ≈ 1 if molecular diameters also obey Geometric mean law & is often omitted
This equation (3) when applied to Young’s Equation with omission of φ leads to the relationship:
This term mainly neglected for lack of data, and also can be negligible if θ is large.
This term corrects for adsorption of vapor on the solid (i.e. to the extent that
contact angle is an equilibrium property, the solid must be in Equilibrium with the
With neglect of π° term we have: Saturated Vapor pressure of the bulk liquid)

Data for various liquids on PTFE do cluster well on such a line. Later GOOD
improved his agreement by including Dipole Interaction terms
(intermolecular) 2
 Semi-Empirical Models: NEUMANN Model
According to Neumann’s concept, there is a relationship between γSV , γLV and SOLID/LIQUID interfacial tension, γSL

Neumann observed a systematic variation of γLcosθ with γL for a series of liquids on various polymers
From this data he was able to infer (with neglecting π°) a linear variation of φ with γ SL

Based on this the following equation of state was derived:

….Eq. (1)

α is determined from contact angle data for hydrophobic surfaces. Superscript EOS stands for Equation-of-state

….Eq. (2)

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 Semi-Empirical Models: NEUMANN Model
In combination with earlier γAB this leads to the mathematical model equation:
This eq. can be used in conjunction with Young’s eq. for predictive purposes
Especially to obtain γSV or γS with the knowledge of γLV (or γL assuming the ‘v’
contribution is negligible
General form obtained was:

A second relation (modified version) developed is:

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 Fowkes Approach: Non-polar to Polar wetting system

Fowkes noted that for POLAR Liq. (eg. Water) much of the intermolecular potential generating
γL is due to hydrogen bonding and various dipole interactions and that these should not be
important at WATER-HYDROCARBON interface
> Proposed that : only DISPERSION interactions (i.e. forces) are important at such as interface.
So modified the γAB equation to be:

Example: Water-Hydrocarbon interface

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 Interfaces between Different types of substances with different polarities & GGFY equation
Fowkes Approach: Non-polar to Polar wetting system

For a non-polar Solid or Liquid, the Young’s equation under the Good-Girifalco-Fowkes approximation becomes the GGFY eq.:

Interesting fact !
For both L and S non-polar This theoretical mathematical treatment
provides an interpretation of why water,
a polar liquid behaves towards
Hydrocarbon (HC) as though the surface
were non-polar
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 Interfaces between Different types of substances with different polarities & GGFY equation
Example Problem: Calculation exercise

#1) n-octane liquid on PTFE solid surface

θ = 98°, 112°, 115° →

Thus, the effect of π° term is large in all three cases

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 Interfacial tension, surface tension and fundamental aspects
σ in binary systems can be divided into “non-specific” dispersion component σd and “non-
dispersion” component σn which is determined by the type of intermolecular interaction in the
neighboring phases
Dispersion Interactions in interface
Here A is Hamaker constant, b is If ionization potentials of molecules A
effective intermolecular distance and B are close, the following
frequently used approximation
Total free energy (i.e. interfacial tension) of the interface is given by the relationship is valid:
GGF eqn.
Component of the surface energy
stipulated by the AAB [=] energy [=] kJ or Joule
“uncompensated” non-dispersion αA [=] length3 [=] Å3
interactions in the interfacial nA [=] (moles)⋅length-3 [=] (moles)(cm-3)
layer between 1,2 phases

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 Interfacial tension, surface tension and fundamental aspects

Interface between two Liquids: Following Empirical rule holds in general ⇒ Antonow’s rule

σ12 equals the difference between the surface tensions of more polar and less polar liquids: = σ 1 − σ2

For two mutually soluble liquids the values of σ1 and σ2 correspond to the surface tensions of
their saturated solutions.
This is valid especially for “POLAR” liquids, as the surface tension can be significantly lowered by
addition (dissolution) of a non-polar (or less polar) liquid (therefore a surface active agent !)
Rule is valid with a high degree of accuracy for interfaces between various organic liquids and their
aqueous solutions