Interfacial Engineering

PECE515
Calcutta University

Non-DLVO Forces

Dr. Sudeshna Saha

Assistant Professor
Chemical Engineering Department
Jadavpur University
Born Energy
• When a single ion in a vacuum or in a medium, even
though not interacting with other ions, still has an
electrostatic free energy associated with it
• This energy equal to the electrostatic work done in forming
the ion that in a vacuum - referred simply as the self-
energy.
• while in a medium referred as the Born or solvation energy
of the ion.
• it determines among other things the extent to which ions
dissolve and partition in different solvents
 ro to its full charge Q. At any stage of this process let the ioni
rge Q. At any stage of this process let the ionic
incremented by dq. The work done in bringing this additio
char
y dq.
¼ The workfrom
a is therefore, done Eq.in bringing
(3.3), puttingthis
Q1 ¼additional
q, Q2 ¼ dq, chan
Born
e, from Energy/Repulsion
Eq. (3.3), dq1 ¼ q, Q2 ¼ dq, and r ¼
puttingq Q
dw ¼
q dq 4p30 3a
dw ¼
ree energy of charging
4p30 3a the ion, the Born energy, is
Z Z Q 2
harging
i the ion, the Born
q dq energy, is Q2 ðzeÞ
m ¼ dw ¼ ¼ ¼ :
Z 0 4p30 3a 8p30 3a 8p30 3a
Q 2 2
q dq Q ðzeÞ
wgives
¼ the electrostatic
¼ free energy
¼ of :an ion in a medium o
• The
0 4p3
Born 0 3a
energy 8p3
gives the
0 3a 8p3
electrostatic
0 3a
free energy of an ion in a
sitive because the energy is unfavorable; that is, it is the energ
medium of dielectric constant ε.
ributed
ostatic onsmall
the energy
• At veryfree
surface of a sphere against its own electrostati
interatomic distances, the electron clouds of of
of an ion in a medium diele
atoms
gy can
he energyalso
overlap, be
and
is obtained
there arises
unfavorable; from
a the
strong
that energy
repulsive
is, it is of
force
the the
that electric field
determines
energy of kee
how close two atoms or molecules can ultimately approach each
ostatic theory (Guggenheim, 1986; Landau and Lifshitz, 198
surface
other of a sphere
- known as the against its own
Born repulsion electrostatic repul
for ions
an electric field E arising from a charge or any distribution
obtained from the
volume. Thus, in general,
energy of the electric field of the
Water is such an unusual substance that it has been
accorded a special place in the annals of phenomena
dealing with intermolecular forces, and two types of
“special interactions”—the hydrogen bond and the
hydrophobic effect—are particularly relevant to the
interactions of water.

For a liquid of such a low molecular weight, water has

unexpectedly high melting and boiling points and
latent heat of vaporization.
Hydrogen Bonding Chapter 8 • Special Inte

• The intra- molecular O–H distance about 0.10

nm,
(a) (b)
• but the intermolecular O…..H distance is only H
0.176 nm, H O H N

O H C C H
• much less than the 0.26 nm expected from H
O H
N H O
summing the two van der Waals radii but larger H
than the covalent distance of 0.10 nm
• Thus, the intermolecular O….H bond is (c)
implicated, which at first sight appears to R
possess some covalent character O F F
H H H H H
O F
• Such bonds known as hydrogen bonds
R
(repeat unit)
• Not unique to water
• they only involve hydrogen atom (d) (e) (f)
R R O H O
−
O H O
• by virtue of their tendency to become positively C C O C C O
R C C R
polarized and their uniquely small size, can O H O
O O
C C
H
interact strongly with nearby electronegative H H

atoms, resulting in an effective H-mediated

FIGURE 8.2 Different types of hydrogen bonds and hydrogen-bonded structures. Linear hydrogen
“bond” between two electronegative atoms
lowest energy, but some H bonds with a —H$$$ angle of 20! or more also occur (cf. Figure 8.3). (a
dimensional structures (e.g., ice). (b) Two-dimensional (layered) structures (e.g., formamide). (c) O
(chain and ring) structures (e.g., alcohols, HF). (d) Dimers (e.g., fatty acids). (e) Intramolecular H bo
Characteristics of H-bonds
• the hydrogen bond predominantly an electrostatic (Coulombic)
interaction
• With few exceptions, the H atom not shared but remains closer to
and covalently bound to its parent atom
• Accordingly, the hydrogen bond between two groups XH and Y is
usually denoted by X–H….Y.
• Certain characteristics of hydrogen bonds do make them appear like
weak covalent bonds. For example, they are not only fairly strong
but also fairly directional
• This endows them with the ability to form weak three- dimensional
“structures” in solids, whereas in liquids the short-range order can
be of significantly longer range whenever hydrogen bonds are
involved
• No simple equation for interaction potential-one does find that the
strengths of hydrogen bonds tend to follow a 1/r2 distance
dependence
The Hydrophobic Effect

• The strong inclination of water molecules to form H-bonds

with each other influences their interactions with nonpolar
molecules that are incapable of forming H-bonds (e.g.,
alkanes, hydrocarbons, fluorocarbons, inert atoms, vapor).
• When water molecules come into contact with such a
molecule or small vapor cavity (bubble), they are faced
with an apparent dilemma: no matter in which direction
the water molecules face, it would appear that one or
more of the four charges per molecule will have to point
toward the inert solute molecule and thus be lost to H-
bond formation.
•
 (a)

Tetrahedrally Dodecahedron
coordinated
water molecules

14-hedron 16-hedron
(Tetrakaidecahedron) (Hexakaidecahedron)

(b) WATER

HYDROPHOBIC OR VAPOUR INTERFACE

FIGURE 8.5 (a) “Clathrate cages” and “gas hydrates” (Holder et al., 2001) formed by water molecules around small
• The immiscibility of inert substances with water, and the
mainly entropic nature of this incompatibility, is known as
the hydrophobic effect and such substances (e.g.,
hydrocarbons and fluorocarbons) are known as
hydrophobic substances
• hydrophobic surfaces do not get “wetted” by water; when
water comes into contact with such surfaces, it rolls up
into small lenses and subtends a large contact angle on
them
The Lotus Effect: super hydrophobic surfaces

lotus leaf
repels even
honey and glue