On Variational Principles for Irreversible Processes

Philip Rosen
Citation: J. Chem. Phys. 21, 1220 (1953); doi: 10.1063/1.1699167
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THE

JOURNAL

OF

CHEMICAL

PHYSICS

VOLUME

21,

NUMBER

JULY,

1953

On Variational Principles for Irreversible Processes*

PHILIP ROSEN

Applied Physics Laboratory, The Johns Hopkins University, Silver Spring, Maryland
(Received January 26, 1953)

A variational principle is formulated for diffusional processes such as heat and matter diffusion which is a
modification of Onsager's principle of minimum dissipation. Also a variational principle is given for the flow
of viscous incompressible fluids which has some analogy to Onsager's principle.

If the integral f (J212O')dT is stationary, subject to the

equation of continuity VJ+pC"lJTlat=o, with the
surface current J n, T and aTI at specified, then

I. DIFFUSIONAL PROCESSES

ONSAGERl has defined a dissipation function

1
q;(J, J)=-L: RidJk
2T ik

(1)

which is one-half of the rate of production of irreversible

entropy. The currents or fluxes J are related to the
generalized forces X by
(2)

where Rik is the symmetric generalized resistance

tensor.
Onsager has shown that if the integral of the above
dissipation function over a volume T is a minimum,
subject to continuity conditions on the currents, the
specification of the currents on the boundary and with
the forces specified, then Eq. (2) is obtained.
In the case of steady heat flow in an isotropic medium,
q;=RJ2/2T,

X=-VTIT.

yields
and X can be interpreted as the temperature T except
for a possible additive constant whose effect on the
resultant differential equation is nil. Thus far this is
analogous to Onsager's principle. However the above
variational principle is not as useful as it could be, since
the temperature T must be held fixed when the current
J is varied. We wish to vary T alone. We find, by using
Eq, (5), that the integral in Eq. (4) becomes
1=

J[

O'(VT)2
(aT
)]
- 2 - - T pC'a;-V.O'V'T dT.

By virtue of Green's theorem we have

In this case Onsager's principle of least dissipation

would be
RJ2
)
( 2T +XV J dT=O,

(5)

J=-O'VX=-O'VT,

TO'V'2TdT=-

VTV'(O'T)dr+ f TO'::dS.

(3)

Thus

with the heat current on the boundary J n fixed and T

specified. The Euler LaGrange equation equivalent to
Eq. (3) is then
RJIT='VX,
where the LaGrange multiplier X is interpreted as liT.
The purpose of this note is to show that in simple
problems of heat flow or matter diffusion, one can define
another dissipation function, 1/I=J2/2O', where the conductivity O' is the ordinary thermal conductivity for
heat flow or the ordinary diffusivity for matter diffusion.
The function 1/1 will lead to simpler variational principles
if we assume that O' is only a function of spatial coordinates. We shall consider only the case of nonsteady heat
flow in isotropic media here. The case of matter diffusion will follow by analogy.

1= -

J[

O'
aT] dT+
-(V'T)2+pC.T2
at

aT
TO'-dS.
an

(6)

If U=O subject to the condition that Un=O and that

aTI at is specified, we have
.

U=-

f[pC.:~~T+O'VT'V~T]dT

f O'~TdS+ J

TO'(

~)dS.

Also

O'V'T V~TdT=

VT V(O'~T)dT-

(V'T VO')~TdT

,.. This work was supported by the Bureau of Ordnance, U. S.

Navy, under Contract NOrd 7386.
1 L. Onsager, Phys. Rev. 37, 405 (1931).

1220

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VARIATIONAL PRINCIPLES FOR

Thus
0/= -

J (Cv:{;-V'UVT )aTdr=O,

since U ,,=0. Consequently since aT is arbitrary,

aT
CvP---= V' uVT.
at

(7)

Now the surface integral in Eq. (6) has no effect on

the differential equation obtained from the variational
principle since it is equivalent to the volume integral of
a divergence. 2 The only influence the surface integral
has is to change the boundary conditions. If we omit
the surface integral, we find that the variation,

IRREVERSIBLE PROCESSES

variational principle similar to Onsager's in which

forces are held fixed.
Let us consider the minimization of the dissipation of
energy subject to the condition that energy and mass be
conserved, with the acceleration at every point specified
and the fluid velocity specified at the boundary. If q is
the velocity and u, v, ware the components, then the
conservation of energy yields

Jq.p.ndS= Jpq.Adr+ if?dr,

<I>=7J [2 (

where II'n(X, y, z) is an orthonormal set of functions

which can be used to satisfy the bOundary conditions.
Then we will be able to carry out the above variations
with the an as variables holding da n / dt fixed. In the
case of convection, the mobile derivative, DT/Dt
= aT/ at+q VT replaces aT/at and is held fixed in
carrying out any of the above variations. Here q is the
velocity of the medium.

Millikan attempted to obtain a variational principle

for describing the flow of a viscous incompressible fluid
and came to the conclusion that for three-dimensional
flow, unless the vector product of the vorticity and
velocity is zero, such a principle could not be found. He
however overlooked the possibility of a restricted
2R. Weinstock, CaJculus of Variations (McGraw-Hill Book
Company, Inc., New York, 1952).
3 C. B. Millikan, Phil. Mag. 1, 641 (1929).

aU)2 (aV)2 (aW)2

ax +2 -a; +2 a;:

+ (aw + aV)2+ (au + aW)2+ (av + au) 2],

ay az
az ax
ax ay

(10)

where 7J is the viscosity. Since p is constant, the conservation of mass is simply V q = O.

If we omit the surface integral in Eq. (9) (since it
only affects boundary conditions), then we can state the
variational problem as

of (~-Xpq'A-)J.(x, y, z)Vq )dr=O,

(11)

A and q on boundary fixed.

Here Xis an undetermined LaGrangian multiplier and
)J.(xyz) an undetermined function. The Euler LaGrange
equivalent to Eq. (11) is then

-'ApA= - V)J.(x, y, z)+7JV, Vq.

n. INCOMPREssmLE VISCOUS FLUID

8

(9)

where P is the stress tensor, n is the unit normal to the

surface S, p is the fluid density, A is the local acceleration = Dq/Dt, and if? is the dissipation of energy per unit
volume. The function4 if? for an incompressible fluid can
be expressed as

(8)
with aT/at fixed and T specified on the boundary leads
to Eq. (7).
In using either Eq. (8) or its counterpart containing
the surface integral for approximate calculations, one
can expand the temperature in the series

1221

Thus we take X= -1 and )J.= p= the hydrostatic pressure, and the Navier-Stokes equation is obtained.
The author wishes to express his appreciation to Dr.
F. T. McClure of the Applied Physics Laboratory and to
Professor S. Corrsin of The Johns Hopkins University
for stimulating discussions of the subject matter of this
note.
4

H. Lamb, Hydrodynamics (Dover Publications, New York,

1945).

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