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8/24/2015

Meeting at the Interface

Finding your place between phases

Scale Matters

Weve already talked some about interfaces


and thin films
What are typical dimensions of thin films?

Since this is close to the size of many molecules,


molecular interactions are usually influential, and
often controlling

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Module Objectives

Identify causes of structuring which result in


unique interfacial properties
Determine whether certain molecular
interactions are likely to cause structuring
Summarize products and product
characteristics impacted by interfacial
properties
Evaluate the magnitude of overlap and
Coulombic forces between molecules

Your Book is Wrong sort of

This chapter is best read starting with the last


section
The importance of this chapter is not being
able to calculate intermolecular forces
You will still need to do this
The importance of this chapter is using those
forces to determine when the interface
behaves differently from the bulk

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How do fluids normally behave

Consider this liquid


hexanol
The motion is normally
random
Each polar, aliphatic
molecule is only
influenced by like
molecules
Energy is thermal,
described by kT

How do fluids at interfaces behave?

The molecular forces are


now non-uniform since
molecules at the interface
are exposed to two different
electronic environments
If there is a certain balance,
there will be structuring at
the interface
The energy of the system
will be described by the
sum of the forces between
molecules, V

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When are interfacial properties important?

It depends on the ratio


of the interaction
energy between
Vij
molecules to the
thermal energy of the
system
kT

The Boltzman equation

Guide to determine molecular ordering

molecular ordering exp- Vij kT

The V term takes many forms, depending on


the types of interactions present

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How Repulsive!

Molecular interactions are the net sum of


attractive and repulsive forces in along a
particular vector
The magnitude and direction of these forces
depend upon the electrical field exhibited by
the molecule
This field, or electron cloud, is subject to
distortion by other molecules

If you really wanted to

You could solve the Schrdinger equation for


the interaction energy between molecules
OK for simple molecules
A more useful way is to describe the forces in
classical terms when possible, use quantum
when necessary, and then sum the terms

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Basic Molecular Interactions

Charge Transfer
Multipole/multipole (polar molecules)
Multipole/induced multipole
Dispersion (induced multipole/induced
multipole)
Overlap interactions (collisions)

Some forces are non-exclusionary

Some of these interactions are limited to


certain types of molecules
Permanent dipoles
Metals
Others occur in all molecules
Dispersion forces
Overlap

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Overlap Forces

When molecules get too close, their electron fields


overlap
Like charges repel
n
R
Voverlap ( R)

This is how molecular radius is defined

Coulombic Interactions

We can determine the interaction energies for


charged bodies using classical analysis
q2 q1
F
4 0 1 R122

V Fdr
R12

This approach works for ion-ion, ion-dipole,


and dipole-dipole

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Some Calculus Happens

Monopole-monopole interactions are strong


compared to thermal energy

Monopole-dipole interactions usually are stronger


than thermal energy, but depend on the dipole
moment and orientation

Dipole-dipole are even more strongly dependent on


orientation, so are often less intense compared to
thermal energy
Quadrapole interactions are even less intense and
more angle dependent

Orientation (of Matter) Matters

In this case, V is
a function not
only of
separation
distance R but
of the angle of
approach

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Comparing maximum energies of


Coulombic interactions

What this means

In the gas phase, only very polar molecules


are aligned by dipole-dipole interaction forces
When dipole interaction energies are
comparable to kT, dipoles rotate freely with
respect to each other
In liquids and solids, Coulombic interactions
are weaker and dipole-dipole interactions do
not lead to alignment, so the contributions to
the overall energy (V) must be angle
averaged

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Angle what?

If you consider every possible orientation of


the molecules you can find the average
energy overall
The mean value theorem gives us the
calculus tool
Boltzmann gave us the overall method

Angle averaged values are always attractive,


and they decrease as T increases

Some of these forces are of particular


interest (van der Waals)
Dipole-Dipole interactions when averaged
over all possible angles
Keesom interaction V 1 R6

Dipole-Induced Dipole interactions when


averaged over all possible angles
Debye interaction V 1 R6

Dispersion Forces
London forces (Lifshitz in condensed phases)
V 1 R6

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And on a related note, Colloids

Colloids are systems in which particles are


dispersed (possibly metastable) in another
phase
Name your favorite colloid!
For a colloid to exist, think about what must
be balanced
Gravity
Drag
Kinetic energy

These are a few of our favorite things

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Same thing, just smaller

On a molecular scale, the important thing


becomes intermolecular forces
Particles WILL collide
Will they stick? Bounce? Leave a path of
destruction?
Consider the forces at work
Coloumbic
Dispersion
van der Waals and related forces
Kinetic (kT)

Why? Just tell me why?


Shape
Wetting
Vapor pressure

http://www.chemicool.com/elements/mercury.html

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Making Water Do Tricks

http://pubs.acs.org/doi/abs/10.1021/la063376k

Theyre Everywhere

Latex products Wine & Beer


Photography Building Materials
Farming Automotive products
Detergents Cosmetics
Foods Spray drying
Minerals Multiphase
Paper separations
Plastics Multiphase reactions

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Next time

Induced Interactions
Dispersion

van der Waals Forces

Application to particle interactions


Hamaker constant

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