19. Boundary Conditions 131
phase boundary is approached from the liquid side, these attractive forces are not
felt equally because there are many fewer liquid phase molecules near the phase
boundary. Thus there tends to be an unbalanced attraction to the interior of the
liquid of the molecules on the phase boundary. This is called “surface tension”
and its manifestation is a pressure increment across a curved interface. A some-
what more detailed description is provided in texts on physicochemical hydrody-
namics. Two excellent sources are Probstein (1994, Chapter 10) and Levich (1962,
Chapter VII).
H. Lamb, Hydrodynamics (6
th
Edition, p. 456) writes, “Since the condition of
stable equilibrium is that the free energy be a minimum, the surface tends to contract
as much as is consistent with the other conditions of the problem.” Thus we are led
to introduce the Helmoltz free energy (per unit mass) via
F = e − TS, (4.94)
where the notation is consistent with that used in Section 1.8. If the free energy
is a minimum, then the system is in a state of stable equilibrium. F is called the
thermodynamic potential at constant volume [E. Fermi, T hermodynamics, p. 80].
For a reversible, isothermal change, the work done on the system is the gain in total
free energy F ,
dF = de − TdS − SdT, (4.95)
where the last term is zero for an isothermal change. Then, from (1.18), dF =−pdv =
work done on system. (These relations suggest that surface tension decreases with
increasing temperature.)
For an interface of area = A, separating two media of densities ρ
1
and ρ
2
, with
volumes V
1
and V
2
, respectively, and with a surface tension coefficient σ (correspond-
ing to free energy per unit area), the total (Helmholtz) free energy of the system can
be written as
F = ρ
1
V
1
F
1
+ ρ
2
V
2
F
2
+ Aσ. (4.96)
If σ>0, then the two media (fluids) are immiscible; on the other hand, if σ<0,
corresponding to surface compression, then the two fluids mix freely. In the following,
we shall assume that σ = const. Flows driven by surface tension gradients are called
Marangoni flows and are not discussed here. Our discussion will follow that given by
G. K. Batchelor, An Introduction to Fluid Dynamics, pp. 61ff.
We wish to determine the shape of a boundary between two stationary fluids
compatible with mechanical equilibrium. Let the equation of the interface surface be
given by f (x,y,z) = 0 = z − ζ(x, y). Align the coordinates so that ζ(0, 0) = 0,
∂ζ /∂x|
0,0
= 0, ∂ζ /∂y|
0,0
= 0. See Figure 4.23. A normal to this surface is obtained
by forming the gradient, n =∇[z − ζ(x, y)]=k − i∂ζ /∂x − j∂ζ /∂y. The (x, y, z)
components of n are (−∂ζ/∂x,−∂ζ/∂y,1). Now the tensile forces on the bounding