Intermolecular and interparticle forces

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Intermolecular energies

3D Pressure-volume isotherms 2D Spreading pressure-area isotherms
Hirschfelder Fig 4-1-1.gif Gaines Fig 4-7.gif
Hisrshfelder, Fig. 4.1.1 Gaines, Fig. 4.7
The figure at left shows a sample pressure-volume isotherm. Note that the horizontal lines between the liquid and gas phases are an unstable state. The fluid discontinuously transforms from the intersection at one side of the dashed curve to the other (e.g. boiling water undergoes a sudden change from liquid to vapor). The figure on the right shows the spreading of a thin layer of myristic acid on the surface of a liquid. Since the system is two-dimensional, the pressure is replaced by a force per volume (dyne/cm). As the layer is compressed or the temperature is raised, it exerts more pressure along its boundary.

Flow properties from molecular energies

Vicosity at short times.png For short time scales and simple liquids, the viscosity η can be approximated by the product of the instantaneous modulus G0 and the relaxation time τ.
Erying model of flow.png Erying model: When the strain is generated molecules are "trapped" inside an energy barrier of size ε and "jump" to a relaxed state with the characteristic time τ. While inside the barrier, the molecule vibrates with the characteristic frequency ν of the solid. Relaxation time in Eyring model.png
Viscosity with Erying model.png Combining these equations yields the Arrhenius behavior. In this case, ε is the heat of vaporization of the liquid, which is the upper bound of the energy barrier. This behavior can be seen experimentally by plotting the logarithm of viscosity as a function of the reciprocal of the temperature.

Forces near surfaces

  • Bulk phases are characterized by density, free energy and entropy – not by forces.
  • Molecular forces average out.
  • Not so at surfaces.

Galileo Surface Forces.png Galileo reference.png

(Modern) forces near sufaces

  • (a) This potential is typical of vacuum interactions but is also common in liquids. Both molecules and particles attract each other.
  • (b) Molecules attract each other; particles effectively repel each other.
  • (c) Weak minimum. Molecules repel, particles attract.
  • (d) Molecules attract strongly, particles attract weakly.
  • (e) Molecules attract weakly, particles attract strongly.
  • (f) Molecules repel, particles repel.

Israelachvili Fig 10-1.gif
Israelachivili Fig.10.1

Interactions from molecular attraction

Eqn molecular attraction.png
Israelachvili Fig 10-2.gif
Israelachivili Fig.10.2

  • (a) A molecule near a flat surface.
  • (b) A sphere near a flat surface.
  • (c) Two flat surfaces.

Eqn Molecule surface attraction.png
Eqn Sphere Surface Attraction.png
Eqn Surface Surface Attraction.png

Derjaguin Force Approximation

Israelachvili Fig 10-3.gif
Israelachivili Fig.10.3
Eqn Derjaguin Force Equation.png
Eqn Derjaguin Force Equation-II.png

Where W(D)is the energy of interaction of two flat plates.

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