Thermodynamics of

Interfaces
And you thought this was just
for the chemists...

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)
Intensive Variables
P: pressure
Surface tension
T: Temperature (constant)
Chemical potential

Extensive Variables
S: entropy
U: internal energy
N: number of atoms
V: volume
Surface area

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

Chemical Potential
refers to the per molecule energy due
to chemical bonds.
Since there is no barrier between phases,
the chemical potential is uniform
g = a = l =

[2.21]

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
U = Ua + Ug + Ul

[2.25]
[2.26]

How many angels on a pin head?

The inter-phase surface is twodimensional,
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]
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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
The FDF for the system is then the sum of the
three FDFs
TdS = dU + PdV - dN - d

(system)

[2.27]

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

Equation of state for the surface phase (analogous to Pv =

nRT). Relates temperature dependence of surface tension
to the magnitude of the entropy of the surface.

Laplaces Equation from Droplet in Space

Now consider the effect of a curved air-water
interface.
Pg and Pl are not equal
g = l =

Fundamental differential form for system

TdS = dU + PgdVg + PldVl - (dNg+dNl ) - d
[2.31]

Curved interface Thermo, cont.

Considering an infinitesimally small spontaneous
transfer, dV, between the gas and liquid phases
chemical potential terms equal and opposite
the total change in energy in the system is
unchanged (we are doing no work on the system)
the entropy constant
TdS = dU + PgdVg + PldVl - (dNg+dNl) - d [2.31]

Holding the total volume of the system constant,

[2.31] becomes
(Pl - Pg)dV - d = 0 [2.32]

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Droplet in space (cont.)

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]).
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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

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Vapor Pressure at Curved Interfaces

Curved interface also affects the vapor pressure
Spherical water droplet in a fixed volume
The chemical potential in gas and liquid equal

= g [2.37]

and remain equal through any reversible process

dl = dg [2.38]

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Fundamental differential forms

As before, we have one for each bulk phase
TdSg = dUg + PgdVg - gdNg (gas)

[2.39]

TdSl = dUl + PldVl - ldNl (liquid)

[2.40]

Gibbs-Duhem Relations:
SgdT = VgdPg - Ngdg
SldT = VldPl - Nldl

(gas)
(liquid)

[2.41]
[2.42]
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Some algebra
SgdT = VgdPg - Ngdg
SldT = VldPl - Nldl

(gas)
[2.41]
(liquid)
[2.42]

Dividing by Ng and Nl and assume T constant

vgdPg = dg
vldPl = dl

(gas)
(liquid)

[2.43]
[2.44]

v indicates the volume per mole.

Use dg = dl [2.38] to find
vgdPg = vldPl

[2.45]

which may be written (with some algebra)

15

Using Laplaces equation...

or
since vl is four orders of
magnitude less than vg, so
suppose (vg - vl)/vl vg/vl

Ideal gas, Pgvg = RT,

[2.49] becomes

16

Continuing...
Integrated from a flat interface (r = ) to that
with radius r to obtain

where P is the vapor pressure of water at

temperature T. Using the specific gas
constant for water (i.e., = R/vl), and left-hand
side is just Pd, the liquid pressure:

17

Psychrometric equation

Allows the determination of very

negative pressures through
measurement of the vapor pressure
of water in porous media.
For instance, at a matric potential of
-1,500 J kg-1 (15 bars, the permanent
wilting point of many plants), Pg/P is
0.99.

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Measurement of Pg/P
A thermocouple is cooled while its
temperature is read with a second
thermocouple.
At the dew point vapor, the temperature
decline sharply reduces due to the energy of
condensation of water.
Knowing the dew point T, it is straightforward
to obtain the relative humidity
see Rawlins and Campbell in the Methods of
Soil Analysis, Part 1. ASA Monograph #9,
1986
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Temperature Dependence of
Often overlooked that all the measurements
we take regarding water/media interactions are
strongly temperature dependent.
Surface tension decreases at approximately
one percent per 4oC!

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