Professional Documents
Culture Documents
Physical Chemistry of Interfaces
Physical Chemistry of Interfaces
Interfaces
And you thought this was just
for the chemists...
1
Terms
Key Concept: two kinds of variables
Intensive: do not depend upon the amount (e.g., density)
Extensive: depend on the amount (e.g., mass)
2
Phases in the system
Three phases
liquid; gaseous; taut interface
Subscripts
indicates constant intensive parameter
g; l; a; indicate gas, liquid, and interface
Gaseous phase g
Interface phase a
Liquid phase l
3
Chemical Potential
g = a = l = [2.21]
4
Fundamental Differential Forms
We have a fundamental differential form (balance
of energy) for each phase
TdSg = dUg + PgdVg - dNg (gas) [2.22]
TdSl = dUl + PldVl - dNl (liquid) [2.23]
TdSa = dUa - d (interface) [2.24]
The total energy and entropy of system is sum of
components
S = Sa + Sg + Sl [2.25]
U = Ua + Ug + Ul [2.26]
5
How many angels on a pin head?
The inter-phase surface is two-
dimensional,
The number of atoms in surface is
zero in comparison to the atoms in
the three-dimensional volumes of
gas and liquid:
N = Nl + Ng [2.27]
6
FDF for flat interface system
If we take the system to have a flat interface
between phases, the pressure will be the same
in all phases (ignoring gravity), which we denote
P
7
Gibbs-Duhem relationship
For an exact differential, the differentiation may be shifted
from the extensive to intensive variables maintaining equality.
TdS = dU + PdV - dN - d (system)
SadT = d [2.29]
or
8
Laplaces Equation from Droplet in Space
Now consider the effect of a curved air-water
interface.
9
Curved interface Thermo, cont.
Considering an infinitesimally small spontaneous
transfer, dV, between the gas and liquid phases
where Pd = Pl - Pg
We can calculate the differential noting that for a sphere V =
(4r3/3) and = 4r2
[2.34]
which is Laplace's equation for the pressure across a
curved interface where the two characteristic radii are equal
(see [2.18]).
11
Simple way to obtain La Places eq....
Pressure balance across droplet middle
Surface tension of the water about the center of the
droplet must equal the pressure exerted across the
area of the droplet by the liquid
The area of the droplet at its midpoint is r2 at pressure
Pd, while the length of surface applying this pressure is
2r at tension
Pd r2 = 2r [2.35]
so Pd =2/r, as expected
12
Vapor Pressure at Curved Interfaces
Curved interface also affects the vapor pressure
l = g [2.37]
dl = dg [2.38]
13
Fundamental differential forms
As before, we have one for each bulk phase
Gibbs-Duhem Relations:
15
Using Laplaces equation...
or
16
Continuing...
Integrated from a flat interface (r = ) to that
with radius r to obtain
17
Psychrometric equation
20