Thermodynamics with internal state variables

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Thermodynamics with internal state variables

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Citation: The Journal of Chemical Physics 47, 597 (1967); doi: 10.1063/1.1711937

View online: http://dx.doi.org/10.1063/1.1711937

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CRYSTAL STRrCTURE OF ALPHA-OXYGEN 597

in 'Y-Oz, which are 3.41 A. The orientation of the mole-

cules helps to explain the fact that the spacing of (010) This work was supported in part by the National

planes in the C-cell (3.429 A) is less than the spacing Science Foundation Grant GP 5859, the U. S. Army

of the (001) planes (3.748 A), even though the mole- Research Office Grant DA-ARO(D)-31-124-GS42, the

cular centers are not directly above each other along a Office of Naval Research Contract Nom 2121 (11),

line normal to (001). From the figure, it can be seen and facilities provided by the Advanced Research

that there are no 0 4 groups; this absence of dimers is Projects Agency. The assistance of David Schiferl in

also true of the other phases of Oz, as well as of the some of the computations is acknowledged with thanks;

known phases of N 2 , CO, and F z. also helpful discussions with P. M. de Wolff and W. H.

A discussion of the packing of molecules in a-02 and Zachariasen. We are grateful to the referee of this

{1-0z, the a-{1 transformation, and possible faults and paper for suggesting that we give a detailed presentation

twins in a has been submitted for publication else- of the experimental data and some of our computations

where. which are now included in the table and figures.

BERNARD D. COLEMAN

J(ellon Institute, Pittsburgh, Pennsylvania

AND

MORTON E. GURTIN

Department of Mathematics, Carnegie Institute of Technology, Pittsburgh, Pennsylvania

(Received 13 February 1967)

This is a study of the thermodynamics of nonlinear materials with internal state variables whose temporal

evolution is governed by ordinary differential equations. After employing a method developed by Coleman

and Noll to find the general restrictions which the Clausius-Duhem inequality places on response functions,

we analyze various types of dynamical stability that can be exhibited by solutions of the internal evolution

equations. We also discuss integral dissipation inequalities, conditions under which temperatures can

be associated with internal states, and the forms taken by response functions when the material is a fluid.

include completely all the others, and each of the three

In phenomenological theories of the dynamical be- classes of theories has its domain of usefulness. It has,

havior of continua there are several ways of accounting for example, long appeared that the Navier-Stokes

for the dissipative effects which, in addition to heat equations can successfully describe the mechanical

conduction, accompany deformation. The oldest and behavior of water under ordinary conditions. On the

simplest way is to introduce a viscous stress which other hand, when certain polyatomic gases, such as

depends on the rate of strain, as is done in the Navier- carbon dioxide, are studied in shock tubes5-8 and in

Stokes theory of linearly viscous fluids. Another de- sonic absorption experiments,9-11 it is found that, in

scription of dissipation assumes that the entire past an appropriate range of density and temperature, at-

history of the strain influences the stress in a manner tenuation effects occur which can be well described,

compatible with a principle of fading memory.! A not by the introduction of a single and constant bulk

third approach is to postulate the existence of internal

state variables which influence the free energy and 6 H. A. Bethe and E. Teller, Aberdeen Proving Ground Rept.

whose rate of change is governed by differential equa- No. X-117, 1941.

tions in which the strain appears. 6 E. F. Greene, G. R. Cowan, and D. F. Hornig, J. Chern.

Phys.19,427 (1951); 21,617 (1953).

7 F. J. Smiley, E. H. Winkler, and T. K. Slawsky, J. Chern.

1 Here we have in mind the fading-memory postulate intro- Phys. 20, 923 (1952).

duced by Coleman and No1l2 . and recently developed from a set 8 W. Griffith, D. Brickl, and V. Blackman, Phys. Rev. 102,

of elementary axioms by Coleman and Mizel. 4 1209 (1956).

2 B. D. Coleman and W. Noll, Arch. Rational Mech. Analysis 9 G. W. Pierce, Proc. Acad. Sci. Amsterdam 60,271 (1925).

6, 355 (1960). 10 K. F. Herzfeld and F. O. Rice, Phys. Rev. 31,691 (1928).

3 B. D. Coleman and W. Noll, Rev. Mod. Phys. 33, 239 (1961); 11 A survey is given by K. F. Herzfeld and T. A. Litovitz,

36, 1103 (1964). Absorption and Dispersion of Ultrasonic Waves (Academic Press

4 B. D. Coleman and V. J. Mizel, Arch. Rational Mech. Analy- Inc., New York, 1959). See also the critique by C. Truesdell,

sis 23, 87 (1966). J. Rational Mech. Analysis, 2, 643 (1953).

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598 B. D. COLEMAN AND M. E. GURTIN

viscosity, but rather by assuming that the ideal-gas of this type by the second law, in the form of the

law pv=RO holds, with the translational (or "active-

mode") temperature, while accounting, in the consti-

Clausius-Duhem inequality. We then give conditions,

in terms of the thermodynamical functions, for dynami-

tutive equations governing the heat capacity, for the cal stability of equilibrium solutions of the evolution

time required for the transfer of molecular motion equations (1.1). After finding logical relations between

from the translational mode, to one, two, or several the various types of stability which can occur, we

internal modes. This is a classical example of a theory discuss special aspects of the theory, such as integral

of dissipation involving a finite number of internal dissipation inequalities, the assignment of tempera-

state variables; the internal variables being the amounts tures to internal states, and the requirements of in-

of energy associated with the various modes of molec- variance. We conclude our study by illustrating the

ular motion. At elevated temperatures the ideal-gas general theory with its simplest nontrivial special case:

law may fail due to chemical dissociation or ionization; ideal gases with a single internal mode of molecular

the finite rates of the reactions of decomposition and motion.

reassociation can then also give rise to pressure-volume

relaxation phenomena. 12 2. THERMODYNAMIC PROCESSES

Recent experience in high-polymer physics shows We consider a body CB with material points X and

that the mechanical behavior of many materials, in- assume that the mechanical forces acting on CB can

cluding polymer melts and solutions, is more easily always be resolved into a body force field and a sym-

described within the general theory of materials with metric stress field. In particular, body couples, couple

fading memory than by theories of the viscous-stress stresses, and multipolar interactions of higher order

type, which do not account at all for gradual stress are assumed absent. We also assume there is no dif-

relaxation, or by theories which rest on a finite number fusion of mass in CB, but CB may deform and conduct

of internal state variables and which, therefore, give heat. Thus, a thermodynamic process for CB is described

rise to discrete relaxation spectra when linearized. by nine functions, of X and the time t, whose values

Using an approach to the thermodynamics of con- have the following physical interpretations:

tinua proposed by Coleman and Noll,1a Coleman and

Mizel14 have found the restrictions the second law (1) The spatial position X= 2C(X, t) in the motion 2C.

places on a class of theories of the viscous-stress type. (2) The symmetric Cauchy stress tensor T=T(X, t).

Later, Coleman15 developed a general theory of the (3) The specific body Jorce b= b(X, t) per unit mass

thermodynamics of materials with fading memory. Here (exerted on CB at X by the external world, i.e., by other

we discuss phenomenological theories of dissipation bodies which do not intersect CB).

which rest upon evolution equations for internal state (4) The specific internal energy E=E(X, t) per unit

variables; we attempt to unify such theories by using mass.

the methods developed in Refs. 13 and 14 together (5) The heatflux vector q=q(X, t).

with techniques from the stability theory of nonlinear (6) The heat supply r=r(X, t) per unit mass and

differential equations. We consider materials for which unit time (absorbed by CB at X and furnished by

the basic local mechanical and thermal variables, such radiation from the external world).

as the stress tensor T, the heat flux vector q, the (7) The specific entropy 7]=7](X, t) per unit mass.

specific Helmholtz free energy 1/;, and the specific en- (8) The absolute temperature O=O(X, t) >0.

tropy 7], are determined through constitutive equations (9) The internal state vector 0:= o:(X, t) = (aI, a2, "',

when the following "state variables" are known: The aN); the numbers a,=a,(X, t) are the internal state

temperature 0, the deformation gradient F (or the variables ,16

"strain"), the temperature gradient gradO, and a set Such a set of nine functions, defined for all X in CB

of N internal or "hidden" state variables (aI, "', aN)' and all t, is called here a thermodynamic process in

We allow the rate of change of each of the ai to be CB if and only if it is compatible with the law of balance

governed by a (generally nonlinear) function Ji of 0, oj linear momentum and the law of balance oj energy.

F, gradO, and the complete internal state (aI, "., aN) : Under sufficient smoothness assumptions, the familiar

ix, =Ji(O, F, gradO, aI, ... , aN), i= 1, .. , N. (1.1) integral forms of these laws are equivalent to the field

equations

We first seek the general restrictions placed on theories px-divT=pb (2.1)

12 See, for example, the discussion of M. J. Lighthill, J. Fluid

and

Mech. 2, 1 (1957). Apparently, the first paper expressing this pe-TL+divq=pr. (2.2)

idea is that of A. Einstein, Sitzber. Akad. Wiss. Berlin Math.

Phys. Kl. 380 (1920). Here p is the mass density, L= grad! is the velocity

13 B. D. Coleman and W. Noll, Arch. Rational Mech. Analysis

13, 167 (1963). 16 Our present pair (F, .. ) forms a vector which Truesdell and

14 B. D. Coleman and V. J. Mizel, J. Chern. Phys. 40, 1116 Toupin,'7 pp. 615-647, call the thermodynamic substate.

(1964). 17 C. Truesdell and R. A. Toupin, "The Classical Field Theo-

lliB. D. Coleman, Arch. Rational Mech. Analysis 17, 1, 230 ries," in Encyclopedia of Physics, S. Fhigge, Ed. (Springer-Verlag,

(1964). Berlin, 1960), Vol. 3, Pt. 1.

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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E VAR I ABL E S 599

gradient, and TL is the inner product of T and L; off the following implications of the Clausius-Duhem

i.e., TL=Tr TLT with LT the transpose of L. Since inequality:

grad and div are the gradient and divergence with

respect to x keeping t fixed, these operators refer to

7j~0 whenever F=O, i=O, and g=O, (3.4)

spatial derivatives. A superposed dot denotes the ma- i~O whenever F=O, 7j=0, and g=O. (3.5)

terial time derivative, i.e., the derivative with respect

to t computed keeping X fixed. The specific free energy I/; (also called the "Helm-

To specify a thermodynamic process it suffices to holtz free energy per unit mass") is defined by

prescribe the seven functions ~, T, , q, 7], 0, and a. (3.6)

The remaining functions band r are then determined Since

by (2.1) and (2.2).

In continuum physics one usually identifies each

material point X with its position X in a fixed reference (3.3) can be written

configuration ffi and writes x = X (X, t). The gradient 0"1= -~-1]O+SF_(p8)-lq.g, (3.8)

F of 2C(X, t) with respect to X,

and hence (3.2) yields also

F=F(X, t) = GRAD2C(X, t), (2.3)

~~O whenever F=O, 0=0, and g=O. (3.9)

is called the deformation gradient at X (or at X)

relative to the configuration ffi. We consistently use 4. CONSTITUTIVE ASSUMPTIONS

the notation GRAD for the gradient in ffi, i.e., the

gradient with respect to X. For a scalar field over (lS, In the present theory the material at the point ~X is

such as 0, an elementary chain rule yields characterized by five response functions, if;, ii, S, q,

and f, which give 1/;, 'T}, S, q, and Ii at X when F, 0, g,

GRADO=FT gradO. (2.4) and a are known at X:

Since gradO occurs frequently in thermodynamics it is 1/;=if;(F, 0, g, a), ( 4.1)

convenient to have a single symbol for this vector.

We use the abbreviation 1]=fJ(F, 0, g, a), (4.2)

q=q(F, 0, g, a), ( 4.4)

Because we assume that x(X, t) is smoothly in-

vertible in its first variable, the inverse F-l of F exists, li=f(F, 0, g, a). (4.5)

and the velocity gradient L=grad:ic is given by

The superposed caret in if;, fJ, 8, and q serves to dis-

L=FF-I. (2.6) tinguish these functions from their values. Since for a

given process the value of F depends not only on X

Let us call the tensor S, defined by and I, but also on the choice of the reference configura-

S=p-lT(FT)-r, (2.7) tion ffi, the form of each of the response functions

depends on ffi. In a materially inhomogeneous body

the Piola-Kirchoff stress tensor. Using this tensor we the functions if;, fJ, S, q, and f will also vary with the

can write (2.2) in the form material point Xj although we do not render explicit

pi-pS.F+divq=pr. (2.8) this possible dependence of response functions on X,

all the arguments we give here are valid equally for

3. THE CLAUSIUS-DUHEM INEQUALITY materially homogeneous and materially inhomogeneous

bodies.

When q/O is regarded to be a flux of entropy due to We say that a thermodynamic process is admissible

heat flow and r/O a supply of entropy from radiation, if it is compatible with the constitutive equations

the specific rate "I of production of entropy is given by (4.1)-( 4.5).

P'Y=p7j-[(pr/O) -div(q/O)]' (3.1) Of course, in assuming (4.1) -( 4.5) we are using

Truesdell's principle of equipresence, which asserts that

The Clausius-Duhem inequality asserts that the rate a quantity present as an independent variable in one

of production of entropy is not negative: constitutive equation of a material should be so present

in all, unless its presence contradicts some general

'Y~o. (3.2)

law of physics or the assumed symmetry of the ma-

For each thermodynamic process the energy-balance terial,l8,19 In the following section we follow the ap-

equation (2.8) permits us to write (3.1) in the form C. Truesdell, J. Pure App!. Math. 30,111 (1951).

18

C. Truesdell, App!. Mech. Rev. 12, 75 (1959), reprinted

19

'Y=7j- (i/O) +o-lS.F- (1/p82) q. g. (3.3) with additions in Applied Mechanics Surveys (Spartan, Washing-

ton, D.C., 1966), pp. 225-236; see also C. Truesdell and R. A.

From this equation and the inequality (3.2) we read Toupin,'7 pp. 703-704.

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600 B. D. COLEMAN AND M. E. GURTIN

proach of Coleman and MizeI14 20 who regarded the solution a= a(X, t) of (4.S) for all t in some interval

Clausius-Duhen inequality as included among the laws [to, to+rJ with a(X, to) = ao(X). Then, using the con-

of physics which can cause a separation of effects, stitutive equations (4.1) -( 4.S) we can compute 1/;, 'T/,

i.e., which can be used to show that certain response f=1/;+e'l], S, and q at each X for all t in [to, to+r]'

functions must be independent of certain variables. Thus to each sufficiently smooth choice of ao, 2C, and e

In fact, we shall show that the derivatives of f, ~, there corresponds a unique admissible thermodynamic

and S with respect to g must be zero. 21 process in ill for some time interval [to, to+r].

Now, let (Fo, eo, go, ao) be an arbitrary point in

5. CONSEQUENCES OF THE SECOND LAW the domain of the response functions f, n, S, q, and f

Within our present framework the second law of for that material point X' of ill which occupies the

thermodynamics is given a precise mathematical mean- place X' in CR. Choosing arbitrarily a time to, a tensor A,

ing by the following postulate of positive production of a vector a, and a scalar a, we consider the motion 2C,

entropy22: and the time-dependent temperature distribution e de-

Every admissible thermodynamic process in ill must fined by

obey the inequality (3.2) at each time t and for all ma- 2C(X, t) = X'+[Fo+(t-to) AJ[X-X'J,

terial points X in ill.

We now seek the restrictions this postulate places e(X, t) =eo+(t-to)a+[go+(t-to)a}Fo[X-X'J,

on the response functions in our basic constitutive (S.7)

equations (4.1)-(4.5).

It follows from (4.1) that in each admissible process for all X in CR and all f?:. to sufficiently close to to. It

follows from the observation made in the previous

f= (OFf) .F+(oef)()+(ogf) .g+(oaf) a, (5.1) paragraph that the fields shown in (S.7) and the

where initial condition a(X, to) = ao determine an admissible

thermodynamic process in ill for t in some time interval

oe.j;(F, e, g, a) = (oloe).j;(F, e, g, a); (5.2) [to, to+r]. Furthermore, this process has the following

the components of ogf and OFf, relative to an ortho- properties:

normal basis el, e2, e3, are given by F(X', to) =Fo, e(X', to) =eo,

[Ogf(F, e, g, a)];= (oldg.)f(F, e, g, a), g(X', to) = go, a(X', to) = ao, (S.8)

i=1,2,3, and

[oFf(F, e, g, a) ];j= (dloFij)f(F, e, g, a), F(X', to) =A, ()(X', to) =a, g(X ' , to) =a. (5.9)

X' and the time to the equation (5.6) becomes

with gi and Fij the components of g and F; d"f is the

N-vector eo'Y = [S(Fo, eo, go, ao) -dFf(Fo, eo, go, ao)]A

d"f= [oalf, da2f, "', d".vfJ, (5.4) -[def(Fo, eo, go, an) +~(Fo, eo, go, ao) Ja

and, of course, -ogf(Fo, eo, go, ao)a

daf a=da1fal+d"2fa2+" +daNfaN' (5.5) -daf(Fo, eo, go, ao) f(Fo, eo, go, an)

Substituting (5.1) into (3.8) we obtain the following - (poOO)-lq (Fo, eo, go, ao) go, (5.10)

expression for the specific rate of production of entropy

where po is the mass density at X' corresponding to the

in an admissible process:

deformation gradient Fo. It clearly follows from (5.10)

e'Y= (S-dFf) F- (def+'I])() that in order to have 'Y~O at X' and to for every choice

of A, a, and a, we must have

-dgfg-daf a- (11 pO) q. g. (5.6)

Suppose that we are given an initial time to, an

S(F, e, g, a) =dF.j;(F, e, g, a), (5.11)

initial internal state vector ao(X) for each X in CR, ~(F, e, g, a) = -def(F, fJ, g, a), ( 5.12)

a motion 2C of ill, and a time-dependent temperature

distribution e over ill. Suppose further that ao, F=

dgf(F, e, g, a) =0, (5.13)

GRAD2C, e, and g=grade, as functions of X and t, d".j;(F, fJ, g, a) f(F, e, g, a) + (pe)-lq(F, e, g, a) g~O,

are smooth enough to ensure the existence of a unique

(5.14)

20 B. D. Coleman and V. J. Mizel, Arch. Rational Mech. Analy-

sis 13, 245 (1963). where, for convenience, we have dropped the subscript 0

21 A similar result holds in the general theory of materials with

in (Fo, eo, go, (1'0). Since this point was arbitrarily

fading memory; d. Coleman,' Theorem 1, p. 19.

22 See Coleman and Noll.' chosen in the domain of our response functions, we

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THE R 1\1 0 D Y N A 1\1 I C S WIT H I N T ERN A L S TAT E VAR I AB L E S 601

have the following four consequences of our postulate holding for nonzero 0.. Such a resolution is valid,

of positive entropy production22a : however, when the following conditions are met: that

f(F, (J, g, a) be independent of g and q(F, (J, g, a)

(i) The response functions -i-, n, and Sare independent

be independent of a. These conditions do not follow

of g; i.e.,1/;, T/, and S are given by functions of F, e, and

from our general assumptions. Yet, the first condition

a alone,

does often follow from special assumptions of linearity

T/=n(F,fl, a), and material symmetry; therefore, it is worth noting

that

(5.15)

agf(F, (J, g, a) =0 => u(F, (J, g, a) ~O

(ii) -i- determines nthrough the entropy relation (5.12) ;

i.e., for all F, (J, g, and a. (5.25)

(5.16)

It is observed that the role played by u in our present

(iii) -i- determines S through the stress relation (5.11); theory is nearly identical to that played by the quantity

i.e., which Coleman in his articles on materials with fading

(5.17) memoryI5 also denotes by u and calls the internal dis-

sipation. For example, our Eqs. (5.21) and (5.15)-

(iv) -i-, f, and q obey the general dissipation inequality (5.17) here yield the equation

(5.14) .

Jj;=S.F-T/8-(Ju, (5.26)

Conversely, using (5.6) it is easily verified that when

the conditions (i)-(iv) hold every admissible process which has the same form as Eq. (8.1) on p. 22 of

in ffi obeys (3.2). Ref. 15. However, in our present theory, if agf is not

It follows from (2.7) and (5.17) that the symmetric identically zero, u may be negative for certain values

Cauchy stress tensor T is given by the equation of g, albeit (5.22) tells us that u~O whenever g=O.

Using (3.6) we can write (5.26) in the form

(5.18)

(5.27)

and hence is a function of F, e, and a. therefore,

The general dissipation inequality (5.14) implies that

when g=O the internal dissipation inequality, u= -e/(J whenever F=O and ~=O, (5.28)

and

aa$(F, e, a) f(F, e, 0, a) ~O, (5.19)

u=~ whenever F=O and e=O. (5.29)

holds, and when aa1/;f=O the heat-conduction inequality,

Since (2.8) and (5.27) imply

q(F, fl, g, a) g~O, (5.20)

u=~-e-l(r-p-l divq) , (5.30)

holds.

If we define the internal dissipation u by

we also have

u=~ whenever pr-divq =0. (5.31)

u=u(F, e, g, a)

= -e-1aa-i-(F, e, a) f(F, fl, g, a), (5.21) Thus, we can assert that in general u measures the

rate ~ at which the entropy of a material point would

we can write the internal-dissipation inequality (5.19; change if the total rate pr-divq of addition of heat were

in the form set equal to zero. In particular, u=~ whenet'er the strain

u(F, e, 0, a) ~O. (5.22) and energy are held constant momentarily.

Further, we may conclude from (4.5), (5.1), and (5.13) 6. STABILITY OF EQUILmRIUM STATES

that

Throughout this section we focus our attention on one

u= -e-1Jj; whenever F=O and 8=0, (5.23) arbitrary material point X in ffi. A triplet (F*, (J*, a*)

and this result when combined with (3.8) yields with

f(F*, (J*, 0, a*) =0 (6.1)

U='Y whenever F=O, 8=0, and g=O. (5.24)

is called an equilibrium state for the material at X.

One cannot generally resolve the inequality 'Y ~ 0 into The domain of attraction at constant strain and tem-

an internal dissipation inequality aa-i- o.~O holding for perature of an equilibrium state (F*, (J*, a*) is the

nonzero g and a heat-conduction inequality qg~O set D(F*, e*, a*) of all ao such that the solution

22. Note added in proof: We have recently seen a report by K. C. a= aCt) of the initial value problem,

Valanis [Iowa State University Bulletin No. 52J giving a theorem

analogous to this. See also the article by E. T. Onat which will a=f(F*, 8*, 0, a) ( 6.2)

appear in the Proceedings of the JUT AM Symposium on Irre-

versible Aspects of Continuum Mechanics, Vienna, June 1966 (to with

be published). . a(O) = It'Q, ( 6.3)

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602 B. D. COLEMAN AND M. E. GURTIN

exists for all t~O and tends to a*, Donder's form of the equation of chemical equilibrium

for that reaction. 24 .25

a(t)-a* as l_oo. (6.4)

We say that an equilibrium state (F*, 0*, a*) is

An equilibrium state (F*, 0*, a*) is said to be (locally) Lyapunov stable at constant strain and temperature if for

asymptotically stable at constant strain and temperature each e> 0 there exists a 5,> 0 such that every solution

if D(F*, 0*, a*) contains a neighborhood of a*, i.e., aCt) of the differential equation (6.2) with

if there exists a r>O such that every internal state I a(O) - a* I <5, (6.11)

vector ao with I ao- a* I <r is in D(F*, 0*, a*).

Let (F*, 0*, a*) be an equilibrium state for the has the property that

material at X, and let ao be in D(F*, 0*, a*). It follows I aCt) - a* I <e ( 6.12)

from the argument containing Eqs. (5.7) that there for all t~O.

exists at least one admissible thermodynamic process Roughly speaking, (F*, 0*, a*) is Lyapunov stable

with the property that at X at constant strain and temperature if holding F and 0

a(O) = ao, while for all t~O, F(t) =F*, fixed for all t and initially setting the internal state

vector a sufficiently near to a* guarantees that a will

OCt) =0*, and get) =0. (6.5) remain near to a* for all t.

It follows from (3.9) that for this process I{;(t) ~I{;(O), Since it follows from (5.19) that for all a

or, by (5.15h, aa~(F*, 0*, a) f(F*, 0*, 0, a) ~O, ( 6.13)

~(F*, 0*, aCt) )~~(F*, 0*, ao). (6.6) ~(F*, 0*, a), as a function of a, can serve as a Lyapunov

function 26 for the equation (6.2), and familiar results

But, since ao is assumed to be in D(F*, 0*, a*), it

follows from (6.4) and the continuity of ~ that in the theory of ordinary differential equations27 yield

the following theorem: Let (F*, 0*, a*) be an equilibrium

lim~(F*, 0*, a( t) ) =~(F*, 0*, a*). (6.7) state and suppose that, in some neighborhood of a*, the

1-+00

following strengthened form of (6.9) holds:

Combining (6.6) and (6.7) we obtain ~(F*, 0*, a) >~(F*, 0*, a*) if a~ a*. (6.14)

~(F*, 0*, a*) ~~(F*, 0*, ao). (6.8) Then (F*, 0*, a*) is Lyapunov stable at constant strain

In words: If the internal state vector a is in the domain and temperature.

of attraction of the equilibrium state (F*, 0*, a*) at If

constant strain and temperature, then the free energy 'Y>O whenever F=O, 8=0, g=O, but ci~O, (6.15)

corresponding to (F*, 0*, a) cannot be less than that

corresponding to (F*, 0*, a*).

then we say that the material under consideration

The following theorem follows at once from (6.8) is strictly dissipative. It is not difficult to show that

(4.5), (5.21), and (5.24) imply the following proposi-

and the definition of asymptotic stability: If (F*, 0*, a*)

is an equilibrium state that is asymptotically stable at

tion: A material is strictly dissipative if and only if the

internal dissipation inequality (5.19) is strict in the sense

constant strain and temperature, then

that

~(F*, 0*, a) ~~(F*, 0*, a*) (6.9) aa~(F*, 0*, a) f(F*, 0*, 0, a) <0 (6.16)

for aU internal state vectors a in some neighborhood of a*, for every triplet (F*, 0*, a) that is not an equilibrium

and, consequently, state.

Suppose that (F*, 0*, a*) is an equilibrium state

aa~(F*, 0*, a) la~a.=O. (6.10) and that (6.16) holds for all a~ a* in some neighbor-

The equation (6.10) may be called the equation of hood m: (a*) of a*; if (F*, 0*, a*) is asymptotically

internal equilibrium. In deriving this equation we have, stable at constant strain and temperature then the

of course, assumed that the variables aI, , aN have argument which gave us (6.8) also gives us the stronger

been chosen so as to be free from constraints of the 24 Th. De Donder, Bull. Classe Sci. Acad. Roy. Belg. 5, 7, 197,

type h( a) =0. Thus, when changes in the internal

state are due to chemical reactions, a.

is not a con-

centration but rather the degree of advancement of the

205 (1922).

25 See, for example, 1. Prigogine and R. Defay, Chemical Ther-

modynamics, Translated by D. H. Everett (Longmans Green and

Co., Ltd., London, 1954), Chaps. 1-4, particularly Eq. (3.29)

ith reaction, in the sense in which the term is used by on p. 40 and Eq. (4.29) on p. 52.

De Donder.23 In this case -aa,I{; is the affinity of the 26 J. Wei, J. Chern. Phys. 36, 1578 (1962), has pointed out that

thermodynamic quantities, such as the free energy, can yield

ith reaction, and the relation aa,I{;=O is just De Lyapunov functions for investigations of stability properties of

chemical reactions.

23 Th. De Donder, Le~ons de Thermodynamique et de Chimie 27 See, for example, P. Hartman, Ordinary Differential Equations

Physique (F. H. van den Dungen and G. van Lerberghe, (John Wiley & Sons, Inc., New York, 1964), pp. 37-40, particu-

Paris, 1920), p. 117. larly Theorem 8.1.

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THERMODYNAMICS WITH INTERNAL STATE VARIABLES 603

it follows from Lyapunov's theorem on asymptotic

stability 28 that if (6.14) and (6.16) hold for all a;t' a* ooif;*(F, 0) =ooif;(F, 0, a)

in a neighborhood of a*, then (F*, 0*, a*) is asymp- +aaif;(F,O, a) aoa(F, 0), (6.19)

totically stable. Combining these observations with the

remark containing (6.14), we obtain the following and a similar formula holds for aFif;. Therefore, the

theorem: Let (F*, 0*, a*) be an equilibrium state with general entropy relation (5.16) and stress relation

the property that (6.16) holds for all a;t' a* in some (5.17), when combined with the equation of internal

neighborhood of a*. Then equilibrium (6.10), yield the equations

(i) (F*, 0*, a*) is asymptotically stable at constant 7]*= -ao.if;*(F*, 0*), (6.20)

strain and temperature if and only if (6.14) holds in

some neighborhood of a*. S* =oF.if;*(F*, 6*), ( 6.21)

(ii) If (F*, 0*, a*) is asymptotically stable at constant

strain and temperature then (F*, 0*, a*) is also Lyapunov and since (6.10) holds at every asymptotically stable

stable under the same conditions. 29 equilibrium state we can assert the following proposi-

tion: If the equilibrium state corresponding to (F*, 0*)

If (F*, 0*, a*) is asymptotically stable, then,

throughout some neighborhood of a*, the only triplet

is asymptotically stable, then ~*(F*, 0*) ix

given by the

equilibrium entropy relation (6.20) and S* (F*, 0*) is

of the type (F*, 0*, a) that is an equilibrium state given by the equilibrium stress relation (6.21).

is the one for which a= a*. [If this were not the case, It follows from the sentence containing (5.20) that

then in each neighborhood of a* we could find an whenever (6.10) holds we have, for all g,

ao such that aCt) == ao satisfies (6.2) and (6.3) but

not (6.4).J Thus we have the following corollary of q(F*, 0*, g, a*) g:$;O. (6.22)

the preceding theorem: Suppose that the material under

consideration is strictly dissipative and let (F*, 0*, a*) Hence this inequality holds for all g whenever (F*, 0*, a*)

be an equilibrium state that is asymptotically stable at is asymptotically stable. The tensor

constant strain and temperature. Then

(6.23)

(i) The inequality (6.14) holds in a neighborhood of a*.

(ii) (F*,O*, a*) is Lyapunov stable at constant strain may be called the equilibrium thermal-conductivity tensor

and temperature. corresponding to (F*, 0*). Since (6.23) and the last

equation of (6.18) yield

For the remainder of this section we assume that

corresponding to each strain-temperature pair (F*, 0*) gq(F*, 0*, g, a*) =g.q*(F, 0*)

there is exactly one internal state vector a* such that

2

(6.1) holds, i.e., such that the triplet (F*, 0*, a*) -gK(F*, O*)g+o(1 g 1 ), (6.24)

forms an equilibrium state for the material at X. The

(6.22) holds for all g only if30

function

a*= a*(F*, 0*) ( 6.17) q*(F*, 0*) =0 (6.25)

determined by this correspondence may be called the and

equilibrium response function for a. Using (5.15) and gK(F*, O*)g~O (6.26)

(4.4) we may construct equilibrium response functions

if;*, ~*, 8*, and q*. These functions give the equilib- for all g. This proves the following theorem: At an

rium free energy if;*, entropy 7]*, stress S*, and heat asymptotically stable equilibrium state the equilibrium

flux q* as functions of only F* and 0*: heat flux vanishes and the thermal-conductivity tensor is

if;* = if;*(F*, 0*) ==if;(F*, 0*, a* (F*, 0*) ), positive semidefinite.

It is a corollary to this theorem that

7]*=~*(F*, 0*) ==~(F*, 0*, a*(F*, 0*,

q =q(F*, 0*, g, a*) =K(F*, O*)g+o(l g\). (6.27)

S*=8*(F*, 0*) ==S(F*, 0*, a*(F*, 0*,

q*=q*(F*, O*)==q(F*, 0*, 0, a*(F*, 0*. (6.18) Thus, at an asymptotically stable equilibrium state

Fourier's law holds to within an error 0 (I g\).

28 See Ref. 27, Theorem 8.2.

29 Usually when one defines asymptotic stability one presup-

poses that the singular point under consideration is Lyapunov 30 This equation can also be obtained using either an argument

stable. Here, however, we have been considering a concept of given by Pipkin and Rivlin 31 or one given by Coleman and Noll13

asymptotic stability that is separate from Lyapunov stability. (pp. 175 and 176).

Thus it is worthwhile for us to observe that Lyapunov stability 31 A. C. Pipkin and R. S. Rivlin, Tech. Rept. No. DA 4531/4,

is actually implied by our weak concept of asymptotic stability from Brown University to the U.S. Army Ordnance Corps,

when (6.16) holds. 1958.

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604 n. D. COLEMAN AND M. E. GURTIN

The heat capacity c is defined by 32 S=aFE(F, 'f/, a). (7.13)

c=ae(F,8, a), (7.1) It follows from (7.11)s and (7.9)3.4 that the general

dissipation inequality (5.14) may be written in the form

where is the response function for the internal energy:

po(F, 'f/, a)aaE(F, 'f/, a) f(F, 'f/, g, a)

(F,8, a) =f(F, 8, a) +8~(F, 8, a). (7.2)

+q(F, 'f/, g, a) g::;O, (7.14)

It follows from the entropy relation (5.16) that

and, in particular,

(7.3)

q=O::::}oaE(F, 'f/, ex)l(F, 'f/, g, a)::;O (7.15)

Henceforth we assume that c is >0 for all (F, 8, a).

Since 8 is >0, this implies that ~(F, fJ, a) is smoothly which is useful for materials which do not conduct

invertible in 8 for each choice of F and a, and we may heat. Of course we also have the following counterpart

rewrite our basic constitutive equations (4.1)-(4.5) in of (5.19) :

the forms oaE(F, 'f/, a) f(F, 'f/, 0, a) ::;0. (7.16)

e= E(F, 'f/, a), (7.4)

According to the definition laid down in Sec. 6, a

8= O(F, 'f/, a), (7.5) triplet (F*, 8*, a*) is called an equilibrium state of

S=S(F, 'f/, a), (7.6) the material at X if and only if it obeys (6.1) at X.

It follows, however, from (7.9)4 that this definition

q=q(F, 'f/, g, a), (7.7) is equivalent to asserting that the triplet (F*, 'f/*, a*)

a=f(F, 'f/, g, a). (7.8) with

'f/*=~(F*,8*, a*), 8*=O(F*, 'f/*, a*), (7.17)

ThefunctionO(F,., a) in (7.5) is just the inverse of

the functi,sm ~(F, ., a) in (5.15)2; the functions E, characterizes an equilibrium state if and only if

S, q, and f are given by

f(F*, 'f/*, 0, a*) =0. (7.18)

E(F, 'f/, a) = (F, O(F, 'f/, a), a}

When (7.18) holds we define the domain of attraction of

=f(F, O(F, 'f/, a), a}+'f/O(F, 'f/, a), (F*, 'f/*, a*) at constant strain and entropy to be the

set D(F*, 'f/*, a*) of internal state vectors ao such that

S(F, 'f/, a) = S(F, Ii(F, 'f/, a), },

the solution a= aCt) of the initial value problem

q(F, 'f/, a) =q(F, O(F, 'f/, a), a),

a=f(F*, 'f/*, 0, a), a(O) = ao, (7.19)

f(F, 'f/, g, a) =f(F, O(F, 'f/, ), g, ex}. (7.9)

exists for all t?,O and approaches a* as t-H/J. We say

It follows from (7.9)1 and familiar chain rules that that (F*, 'f/*, a*) is asymptotically stable at constant

aqE= (aef) (aqO) +o+'f/a~O, strain and entropy if D(F*, 'f/*, a*) contains a neighbor-

hood of a*.

aFE=aFf+(aef) (aFO) +'f/aFO, Since it follows from (7.16) that E(F*, 'f/*, a(t)} is

aa E= (aef) (aaO) +aaf+'f/aaO. (7.10) a decreasing function of t along all solutions of (7.19),

the argument which gave us (6.8) here tells us that

Hence, the entropy relation (5.16) implies that for each a in D(F*, 'f/*, a*)

a~E(F, 'f/, ) = O(F, 'f/, ), E(F*, 'f/*, a)?, E(F*, 'f/*, a*). (7.20)

aFE(F, 'f/, a) =aFf(F, 8, a),

In particular, if (F*, 'f/*, a*) characterizes an equilib-

a"E(F, 'f/, a) =a",f(F, 0, a). (7.11) rium state that is asymptotically stable at constant strain

and entropy, then (7.20) holds for all a in some neighbor-

Of cours~ the number 8 in (7.11h,s is just the tem- hood of a*, and

perature 8(F, 'f/, a) corresponding to F, 'f/, and a.

Equation (7.11h is the expected temperature relation (7.21)

8=avE(F, 'f/, a), (7.12) It of course follows from (7.11)s that (7.21) and

(6.10) are equivalent, i.e., are just different forms of

while (7.11h may be combined with (5.17) to obtain the same equation for a*. This does not, however,

imply that the concepts of stability at constant strain

32 Since both F and IX are held fixed in computing the derivative

m (7.1), the number c may also be called the instantaneous specific

and temperature and stability at constant strain and

!zeat at constant strain (and per unit mass). entropy are logically equivalent: The equation (7.21)

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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E V A R I A B L E S 605

or (6.10) is a necessary, but not a sufficient, condition It follows from the first two of these relations that

for these two types of stability. (7.12) and (7.13) can be written in the forms

We say that a triplet (F*, T/*, a*) obeying (7.18)

8=[a,ii(F, , a)]-I, (8.8)

characterizes a state that is Lyapunov stable at constant

strain and entropy if for each >O there exists a 0,>0 s= -aFii(F, , a)/a,ii(F, , a) = -8a Fii(F, , a). (8.9)

such that every solution a= aCt) of (7.19h having

[ a(O) - a* I <li, also has I aCt) - a* I < for all t';?O. From (8.7)3, (8.9), and (7.11h we obtain

The following proposition is an immediate consequence a"ij(F, , a) = -t11a",E(F, T/, a)

of (7.16) and the theory27 of Lyapunov functions: If

(F*, T/*, a*) obeys (7.18) and has the property that for = -t11a",-f(F, 8, a), ( 8.10)

all a in some neighborhood of a* and hence (7.16) becomes

E(F*,T/*, aE(F*,T/*, a*) whenever arfa*, (7.22) a",ii(F, , a)f(F, , 0, a)';?O. (8.11 )

then (F*, T/*, a*) characterizes a state that is Lyapunov

It follows from (8.2)4 that a triplet (F*, T/*, a*)

stable at constant strain and entropy.

characterizes an equilibrium state, i.e., obeys (7.18)

It follows from (7.11)3, (7.9)4, and the proposition

if and only if the triplet (F*, *, a*) with

containing (6.16) that a material is strictly dissipative

if and only if *=i:(F*, T/*, a*), T/*=ij(F*, *, a*), (8.12)

a"E(F*, T/*, a) 'f(F*, T/*, 0, a) <0 (7.23) obeys the relation

whenever (F*, T/*, a) does not characterize an equilibrium f(F*, *, 0, a*) =0. (8.13)

state.

The last proposition of this section follows from When such is the case, the domain of attraction of

arguments completely analogous to arguments used (F*, *, a*) at constant strain and energy is the set

in Sec. 6: If (F*, T/*, a*) obeys (7.18) and if (7.23) D(F*, *, a*) of all internal-state vectors ao with

holds for all arf a* in some neighborhood of a*, then the property that the solution a= aCt) of the initial

the inequality (7.22) is a necessary and sufficient con- value problem

dition for the state characterized by (F*, T/*, a*) to be n=f(F*, *, 0, a), ( 8.14)

aCO) = ao,

asymptotically stable at constant strain and entropy.

exists for all t';?O and converges to a* as t-HJJ. We

8. INTERNAL ENERGY AS AN INDEPENDENT say (F*, *, a*) is asymptotically stable at constant

VARIABLE strain and energy if D(F*, *, a*) contains a neighbor-

The temperature relation (7.12) and our assumption hood of a*. If for each >O there exists a 0,>0 such that

that 8 is strictly positive imply that the function i: in I a(O) - a* I <li, implies I aCt) - a* I < for all t';?O,

(7.4) is smoothly invertible in its second variable T/. then we say that (F*, t*, a*) is Lyapunov stable at

Hence there exists a function ij such that constant strain and energy.

The next two theorems follow from (8.11).

T/=ij(F, , a), (8.1) If a is in the domain of attraction of (F*, *, a*)

and putting then

O(F, , a) = (j(F, ij(F, , a), a), ij(F*, *, a)::; ij(F*, t*, a*), (8.15)

S(F, , a) =S(F, ii(F, , a), a), Hence, if (F*, *, a*) is asymptotically stable at con-

q(F, , a) =q(F, ii(F, , a), a), stant strain and energy, (8.15) must hold throughout

some neighborhood of a* and

f(F, , a) =f(F, ii(F, , a), a), (8.2)

(8.16)

we can write the constitutive equations (7.5)-(7.8)

as follows: [It follows from (8.10) that the equations (6.10),

O=O(F, , a), (8.3) (7.21), and (8.16), giving necessary conditions for

S= S(F, , a), (8.4) three distinct types of stability that an equilibrium

state may manifest, are equivalent.]

q=q(F, , g, a), (8.5) If (F*, *, a*) obeys (8.13) and if for all a in some

n=f(F, , g, a). (8.6) neighborhood of a*

The equations (7.4) and (8.1) imply that ii(F*, *, a) <ii(F*, *, a*) whenever arf a*, (8.17)

a,ij= (a~E)-I,

then (F*, *, a) is Lyapunov stable at constant strain

aFij+ (a,ii) (aFE) =0, and energy.

(a,ij) (a",E) +a",ij=o. (8.7) We may conclude from (8.10), (8.2)4, and the re-

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606 B. D. COLEMAN AND M. E. CtJRTIN

sideration is strictly dissipative if and only if

$(F*, e(F*, 7]*, a), a)'2.$(F*,8*, a)

a"ii(F*, E*, a) f(F*, e*, 0, a) >0 (8.18)

+[8*-O(F*, 7]*, a) J~(F*, O(F*, 'YJ*, a), a). (9.9)

whenever f(F*, e*, 0, a) r!0.

But

Using arguments given in Sec. 6 one can easily

?)(F*, O(F*, 'YJ*, a), a)=7]*, (9.10)

prove the following proposition which is similar to

the last assertion of Sec. 7: If (F*, e*, a*) obeys (8.13) and, therefore, when (9.9) is added to (9.8) the result-

and if (8.18) holds for_all ar! a* in a neighborhood of a*, ing inequality reduces to (9.7).

then (8.17) supplies a necessary and sufficient condition Using (9.7) we now establish the following theorem:

for (F*, E*, a*) to be asymptotically stable at constant Let (F*, 8*, a*) be an equilibrium state, let 7]* be given

strain and energy. by (9.1), and assume that the strong forms (6.16) and

(7.23) of the internal dissipation inequality hold for all

9. RELATION OF ISOTHERMAL TO ISENTROPIC ar! a* in some neighborhood of a*. If the state (F*, 8*, a*)

AND ISOENERGETIC STABILITY is asymptotically stable at constant strain and tempera-

Let (F*, 8*, a*) be an equilibrium state for the ture, then this state is asymptotically stable at constant

material at X, and let strain and entropy.

Proof: Let (F*, ()*, a*) be asymptotically stable at

7]*=~(F*, 8*, a*), (9.1) constant strain and temperature. Since we here assume

e* = f(F*, 7]*, a*). (9.2) that (6.16) holds for all ar! a* in a neighborhood of a,

it follows from conclusion (i) of the theorem on p. 603

Assuming that the strong forms (6.16), (7.23), and (Sec. 6) that for a in a neighborhood m( a*) of a*

(8.18) of the internal dissipation inequality hold, we

here show that asymptotic stability of the state a,t.a*~$(F*,()*, a$(F*, 8*, a*). (9.11)

(F*,8*, a*) at constant strain and temperature implies It is clear from our lemma (9.7), that (9.11) has the

asymptotic stability of the same state at constant consequence that for a in m( a*)

strain and entropy, and that this latter type of sta-

bility is equivalent to stability at constant strain and ar!a*~(F*,7]*, a(F*,7]*, a*). (9.12)

energy. To prove the first implication we make use

But, since we here also assume (7.23), we may observe

of our assumption that the heat capacity c of Eqs.

that the last sentence of Sec. 7 tells us that (9.12)

(7.1) and (7.3) is positive, i.e., that

is a sufficient condition for asymptotic stability at

a8~(F, 8, a) >0 (9.3) constant strain and entropy of the state characterized

by (F*, 7]*, a*), i.e., the state (F*, ()*, a*), and this

for all F, 8, and a. Using the entropy relation (5.16),

completes the proof.

we can write (9.3) in the form

To show the equivalence of isentropic and isoener-

a8Z/t(F,8, a) <0, (9.4) getic stability we first show that if e*=e(F*, 7]*, a*),

then

which implies that, for each pair (F, a), $(F, 8, a) e*<e(F*,7]*, a) if and only if ii(F*, e*, a) <7]*. (9.13)

must be a concave function of 8:

Indeed, it follows from (8.1) and the positivity of

$(F,8, a) -$(F, 8', a) () that ii(F, e, a) is a strictly increasing function of e

and hence

- (8-8')a8$(F, 8', a) ::;0, (9.5)

or, equivalently, e*<e(F*,7]*, a) if and only if ii(F*, e*, a*)

$(F,8', a) ?:.$(F, 8, a) +(8-8'H(F, 8', a). (9.6) <ii(F*, f(F*, 'YJ*, a), a). (9.14)

Using (9.6) we now prove the following lemma: But since the function ii(F, " a) is the inverse of the

If 7]* is given by (9.1) then function E(F, ., a), we have, for each value of a,

f(F*,7]*, a) -f(F*, 7]*, a*) ii(F*, e(F*, 7]*, a), a)=1)*, (9.15)

?:.$(F*,8*, a) -$(F*, 8*, a*). (9.7) and therefore (9.14) implies (9.13).

Our desired result is now an immediate consequence

It follows from (7.9)1 that of (9.13) and the concluding sentences of Sees. 7 and 8:

e(F*,7]*, a) -f(F*, 7]*, a*) =$(F*, e(F*, 7]*, a), a) When the strong forms (7.23) and (8.18) of the internal

dissipation inequality hold for all a,t. a* in a neighborhood

-$(F*,8*, a*) +[e(F*, 7]*, a) -8*J7]*. (9.8) of a*, an equilibrium state is asymptotically stable at

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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E V A R I A B L E S 607

constant strain and entropy if and only if it is asymp- be a solution of (6.2), and, by our stability postulate,

totically stable at constant strain and energy. we would have a(t)~a*, which is impossible since

aCt) =const~ a*. Conclusion (ii) is an immediate con-

10. INTEGRAL DISSIPATION INEQUALITIES sequence of (9.7), (9.13), and the sentence following

In a body undergoing an arbitrary thermodynamic (6.8) .

process, we may consider, at a given material point, The stability postulate is not a consequence of the

the following general dissipation integrals,33 defined for Clausius-Duhem inequality but is rather an inde-

any two times to<h: pendent hypothesis expected to hold for some materials

but not all. Under this new postulate a single-valued

function a* relates (F*, 0*) to a*, as in (6.17), and

(10.1)

equilibrium response functions ~*, ~*, etc., may be

defined as in (6.18). Of course (6.20)-(6.27) hold,

and the remark following (6.8) here yields

(10.2)

~(F, 0, a) ~~*(F, 0) (10.5)

for all a.

t1

X(tl, to) =

1 to

tr1 {SF-E-(pO)-lqgldt. ( 10.3) Consider now a material point X and a time to,

and suppose that at X the triplet (F, 0, g) has the

following sort of time dependence:

It follows immediately from the law (3.2) of positive

production of entropy and the expressions (3.3) and (F (t), 0(t), g (t) ) = arbitrary values for t < to,

(3.8) for'Y that

= (Fo, 00, 0) for t~to. (10.6)

d (tl, to) ~1J-(tl) -1J-(to) ,

At the time to, the internal state vector a will have a

~(tl, to) ~E(h) -E(to), value ao, determined, through the differential equation

(4.5), by the histories of F, 0, and g up to time to and

X(tl, to) ~'I/(to) -'l/(h). (lOA)

some initial data for a. Although we may not know

The theory we have been developing here can be the value of ao, we do know that for t>to, aCt) will

brought closer to the theory of materials with fading be the solution of (6.2) corresponding to the initial

memory2-4,15 by adding assumptions about the sta- condition aCto) = ao. Since, by our present stability

bility of solutions of the differential equation governing hypothesis, all solutions of (6.2) must approach a* =

the evolution of the internal state vector a. For the a*(Fo, ( 0) we have

remainder of this section we assume the following

lima(t) = a*(Fo, ( 0 ), (10.7)

stability postulate: t_co

Corresponding to each pair (F*, 0*) there is an internal Therefore, it follows from the (tacitly assumed) con-

state vector a* which makes (F*, 0*, a*) an equilibrium tinuity of ~, ~, T, q, and the equations (6.18) and

state that is asymptotically stable in the large at constant (6.25), that at the point X

strain and temperature.

lim1J-(t) =lim~(Fo, 00 , a(t) )=~*(Fo, ( 0 ),

In other words, we assume that given (F*, 0*) there t-ro t-.m

exists at least one a* such that (F*, 0*, a*) obeys lim'l/(t) =lim71(Fo, 00, aCt) )=~*(Fo, ( 0),

(6.1) and also such that every solution of (6.2) obeys

(6.4).

limT(t) =limT(Fo, 00 , aCt) )=T*(Fo, ( 0 ),

This postulate has the following consequences. t-m t-co

(i) Corresponding to each pair (F*, 0*) there is exactly limq(t) =limq(Fo, 00 , 0, aCt) )=0. (10.8)

one equilibrium state (F*, 0*, a*). t-co t-co

(ii) At each equilibrium state (F*, 0*, a*), the in- When a history up to some time to is extended beyond

equalities (6.9), (7.20), and (8.15) hold for all a with to in the manner illustrated in (10.6), we call the result-

'1/* and E* given by (9.1) and (9.2). ing extended history the isothermal static continuation

To demonstrate Conclusion (i) we need merely note of the original history. Equation (10.8) shows, in

that if to a given pair (F*, 0*) there corresponded two effect, that in any isothermal static continuation of an

equilibrium states (F*, 0*, a*) and (F*, 0*, at), arbitrary history, the free energy, entropy, stress, and

both obeying (6.1) with a*~at, then a(t)=a t would heat flux all approach their equilibrium values as t

increases without limit. Moreover, the first of these limits

33 Our present X, d, and .g differ only in the terms containing q

is approached monotonically, for (3.9) here yields

from the functionals which Coleman (on pp. 27, 35, and 39 of

Ref. 15) calls "dissipation integrals." fCt) =:; 0, for all t> to. (10.9)

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608 B. D. COLEMAN AND M. E. GURTIN

The relations (10.5) and (10.8h tell us that the following implications holds for processes which start at

theorem on minimum free energy, originally proven for to from an equilibrium state of the type (10.10), but which

materials with memory,34 has the following form in are otherwise arbitrary:

the present theory, provided we assume that equilib-

rium solutions of (6.2) are stable in the large: Of all F(lt) =F(to), e(to) =e(tr)~t1(tl, to) '2 0,

histories ending with given values of F and 0, the constant F(tl) =F(to) , 1/(to) =1/(tl) =} ~(tl, to)'20,

history with g held fixed at zero and F and 0 held fixed

at the given values gives rise to the least free energy. F(tl) =F(to), f(t O) = f(tl) =}X(tl, to)'20. (10.20)

Thus, our new stability postulate gives the present We call a process isothermal at X if 8=0 at X,

theory many, but not all, the qualitative properties of isentropic if 1]==0 at X, and isoenergetic if f==O at X.

Coleman'sl5 theory of materials with memory. It is clear from (10.1)-(10.3), that the theorem just

Let us now return to the dissipation integrals defined proven has the following corollary yielding inequalities

in (10.1)-(10.3) and consider processes which start for integrals of the stress power in special cyclic

from an equilibrium state, i.e., processes for which we processes36 : Consider a process starting from an equilib-

have at X, rium state of the type (10.10) and for which the tempera-

F(to) =F*, O(to) =e*, ture gradient g is zero for to 5, ts. tl . If the process is

o:(to) = 0:*= a*(F*, 0*), ( 10.10) either isothermal or isentropic, then

tl

but for which F, 0, and g at X are given by arbitrary

functions F(t), O(t), g(t) for t>to. For each such

process, at X

Ft(I)=F(to)=}

I to

SFdt'20. (10.21)

where o:(t) is to be obtained by solving the differential

equation (4.5) with the initial condition o:(to) = 0:*.

11. TEMPERATURES ASSOCIATED WITH

If F and (} return to their initial values F* and e* at

INTERNAL STATES

some time tl > to, then

We here suppose that the first M of the N internal

I/;(tl) =tf(F*, e*, o:(tl)), (10.13)

state variables ai have the same dimension as the

and this equation, when set alongside of (10.11) and specific internal energy . Putting

the consequence (ii) of our stability postulate, implies .'If

that I/; (t1) is greater than if; (to) , fA=f- L:::: a'i, (11.1)

i=l

F(tl) =F*, e(lt) =e*~if;(tO)5,I/;(tl). (10.14)

and

Of course, (10.10) implies that ( 11.2)

(to)=(F*, 0*, 0:*) == *=E(F*, 1/*, 0:*), (10.15) we call fA the specific internal energy of the active mode

and ai, i= 1, 2, M, the specific internal energy of

000,

the ith internal (or "hidden") mode. Defining the func-

If it should happen that F(tl) =F* and 1/(tI) =1/*, then tion 1/# by

M

(tl) =E(F*, 1/*, o:(tr)), (10.17) 1/#(F, A, aI, 0", aM, ~) =jj(F, fA+ L::::a" 0:), (11.3)

i=l

and, therefore, by (10.15) and the consequence (ii)

of the stability postulate, we put

F(tl) =F*, 1/(tI) =1/*~(tO)5,(tl). (10.18) eA = [a'A1/#(F, fA, aI, 000, a']f, ~)]-r, (11.4)

Similarly, ei =[a".1/#(F, fA, aI, 000, a.lf, ~)J\ (11.5)

F(tl ) =F*, f(t 1) =f*=}1/(tO)'21/(tl). (10.19) for i=l, 2, M. We refer to eA as the translational

000,

Combining (10.13), (10.18), and (10.19) with the temperature (or the temperature of the active mode) and

inequalities (lOA), we obtain the following theorem to ei as the temperature of the ith mode. We may observe

on dissipation integralSl5 : that the "temperature of the ith mode" need not be

positive. In fact, as there is at this point no reason to

Under the stability postulate stated above each of the suppose that a".1/#7"'O, we must not rule out the pos-

34 Reference 15, Theorem 3, p. 26.

sibility of ei being infinite.

36 For the corresponding theorem for materials with fading

memory see Remarks 17, 24, and 32 on pp. 27,36, and 39 of 36 For materials with fading memory, analogous results are

Rl;f.1.5, ~iven in Theorem 4/ Remark 2.5, and Remark 3,3 of Ref. 15.

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THERMODYNAMICS WITH J~TERNAL STATE VARIABLES 609

( 11.6) i=1,2,"',N, (11.15)

the temperature relation (8.8) implies that "the tem- then the fact that O=8 i at states of stable equilibrium

perature" 8 is equal to the translational temperature 8A: implies

8=8A. (11.7) O;*(F*, &i*(F*, 0*) )=0*, i=1,2,",M. (11.16)

It also follows from (11.3) that for i=l, 2, "', M,

Since (11.16) must hold for all (F*, 0*), O;*(F*, .)

(11.8) is a left inverse of &i* (F*, .). If we assume, as we shall,

that for every pair (F, ai) we can find a 0 such that

and hence we have the following expression for each 8i :

ai=&i*(F, 8), then we have the following theorem:

(11.9) If the stability postulate of Sec. 10 holds and if the caloric

equation of state (8.1) can be cast in the special form

This formula when combined with (8.16) implies the (11.12), then for each i, i=l, 2, "', M, and for each

following theorem: At an asymptotically stable equilib- fixed F, the function Oi*(F, .) is the inverse of the function

rium state the temperature 8. of each internal mode is &i*(F, .).

equal to the translational temperature 8.'K1 We mav use the foregoing theorem to motivate an

Since 8>0, we conclude from the foregoing proposi- alternativ~ definition of internal mode temperatures

tion that each 8; is strictly positive when the material which is free from the assumption that the a/s have

is close to a state of stable equilibrium. the same dimension as the specific internal energy.

By (11.1), To do this let us drop the assumption that the func-

M tion '1/* defined in (11.3) has the special form (11.12),

i=O if and only if iA+ L a.=O; (11.10) but suppose that the first M of the functions &,* of

i=l

(11.15) are such that, for each value of F, &;*(F, 0)

hence (8.6), (8.11), and (11.9) yield is an invertible function of 0, i.e., that there exist M

a functions CP.* such that

-EA8 + L}.f

;=1

~ ~O whenever i=O,

8;

g=O, and ~=O.

cpi*(F, &;*(F, 0) )=0 (11.17)

(11.11) for all 0>0. When this condition is fulfilled the func-

The inequality (11.11) appears to be in accord with tion CPi* is uniquely determined by the function &i*

intuitive prejudices about properties to be expected and hence by the function f on the right side of the

of temperatures associated with internal modes. constitutive equation (4.5). We call the value

Suppose now that the function '1/* defined in (11.3) (11.18)

has the special form

M of CPi* at an arbitrary pair (F, ai) the temperature of

'I/*(F, tA, aI, "', aM, ~) ='l/A(F, tA, ~) + L

1'=1

'l/i(F, ai). the ith mode corresponding to (F, ai). We continue

to refer to the number entering the constitutive equa-

(11.12) tions (5.15), (4.4), and (4.5) as the translational tem-

perature. As an immediate consequence of (11.17) we

Then 8=8A is given by a function 0* of (F, tA, ~),

have the following proposition: Each CPi shares with Oi

while each Oi is given by a function Oi* of only (F, ai) ;

for (11.4), (11.5), and (11.12) yield

the property of being equal to the translational temperature

oin states of stable equilibrium.

= [O'A'l/A(F, EA, ~)]-\

O=O*(F, EA, ~) (11.13) Unfortunately, the function CPi* is not, in general,

identical to the function (0",'1/*)-1: Although Oi=CPi=O

Oi=Oi*(F, a,) = [o",'l/i(F, ai) J-I. (11.14) at equilibrium, we can expect to have O'i~CPi away

from equilibrium, except, of course, when '1/* has the

Let us assume, in addition, that there exists a function

special form (11.12). As a matter of fact, if CPI* were

a* which assigns to each pair (F*, 0*) an (*, as in (6.17),

equal to [0"1'1/*]-\ then we could conclude from (11.18)

such that the triplet (F*, 0*, 0:*) constitutes an equi-

that 0"1'1/* must be independent of tA and 012,' " a.v,

librium state for the material point under considera-

and hence that

tion. As we saw in the conclusion (i) of the first theorem

of Sec. 10, this assumption is a consequence of the 'I/*(F, EA, aI, "', OIN) ='1/1 (F, Oil) +'l/2(F, EA, 012, " OIN).

stability hypothesis of Sec. 10. If we write (6.17) in

(11.19)

37 This result should be compared with Truesdell's theorem Thus we have the following result: A necessary condition

about the compatibility of total with partial caloric equations of

state for mixtures: C. Truesdell, Rend. Lined 22,33, 158 (1957), that

Theorem IV. (11.20)

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610 B. D. COLEMAN AND M. E. GURTIN

is that the function 7]* have the special form (11.19). tensor Q, the following identities in F, 0, a, and g:

A similar result holds for a2, a3, etc.

In view of the fact that temperatures of internal l/-(F,O, a) =l/-(QF, 0, a),

states are often regarded as definable only in terms of n(F,O, a)=n(QF,O, a),

statistical concepts, we think it worthwhile to make the

following observation. The results of this section sug- QT(F,O, a)QT=T(QF, 0, a),

gest that if we accept the general assumptions made Qq(F, 0, g, a) =q(QF, 0, Qg, a),

here and in Secs. 4 and 5, then the question of whether

we can associate a temperature Oi with a particular f(F, 0, g, a) =f(QF, 0, Qg, a). (12.3)

internal state variable ai becomes one that can be These identities can be used to derive the following

settled on purely phenomenological grounds, namely by reduced forms of our constitutive equations:

inspection of the caloric equation of state and the

equation governing the evolution of ai in a thermo- if;=if;t(C, O, 0:),

dynamic process. 7J=7]t(C,O, a),

12. OBJECTIVITY T=FTt(C,O, a)FT,

response functions l/-, n, S, q, and f of (4.1)-(4.5) a=ft(C, 0, FTg, a), (12.4)

by the postulate of positive production of entropy. where

The principle of material frame indifference,38 which (12.5)

states that an admissible process must remain ad-

missible after a change of frame, imposes further re- is the right Cauchy-Green tensor; of course, by (2.4)

strictions on response functions. and (2.5), FTg is just GRADO. In terms of the response

In our pres en t theory a change of frame is charac- functions introduced here, the entropy relation (5.16)

terized by a time-dependent orthogonal tensor Q. The may be written

scalars 0, , 7], and if; are unaffected by a change of 7]t=-aeif;t (12.6)

frame, but F, g, q, and T transform as follows:

and the stress relation (5.17) becomes

F~QF,

Tt=2pa cif;t. (12.7)

g~Qg,

One might imagine that in some applications a

q~Qq, could represent a vector of dimension three transforming

as a spatial position vector under a change of frame,

T~QTQT. ( 12.1) but such an interpretation for a is not compatible

The manner in which the internal state vector a= with our constitutive equation (4.5). For, if

(ai, " ' , aN) transforms under a change of frame a~Qa, ( 12.8)

depends, of course, on the physical interpretation given

to the components ai of a and therefore varies with then for each time-dependent orthogonal tensor Q, f

the application in mind. For definiteness we assume must obey the identity

here that a is an ordered N-tuple of scalars, each of

which remains invariant upon a change of frame; i.e., (Qa)'=f(QF,O, Qg, Qa), (12.9)

we assume that simultaneously with (12.1) we have

where Q is given by (4.5). Since

a~a. (12.2)

(Qa)'=Qa+Qa=Qf(F, 0, g, a)+Qa, (12.10)

(This is the case, for example, when each ai represents when Q (t) = 1, (12.9) yields

the degree of advancement of a chemical reaction, the

fraction of the total energy in a certain internal mode Qa=O, (12.11)

of molecular motion, or the probability that an internal

degree of freedom is in a particular quantum state.) which equation must hold for all choices of Q at time t.

It follows from (12.2) that the response functions of the But, when Q(t) = 1, the only restriction on Q(t) is that

present theory are compatible with material frame this tensor be skew. Hence (12.11) states that Wa=O

indifference if and only if they obey, for each orthogonal for all skew tensors W, which implies that a=O. In

other words, if a behaves as a spatial three-vector under

38 W. Noll, Arch. Rational Mech. Analysis 2, 197 (1958), who

changes of frame, then (4.5) must be replaced by the

called it the "principle of objectivity of material properties." trivial equations f=O, a=O.

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THERMODYNAMICS WITH INTERNAL STATE VARIABLES 611

13. MATERIAL SYMMETRY, FLUIDS gases with internal molecular relaxation forms an im-

portant special case of our present theory, we give the

The symmetry group S of a material is the set of all reduced forms taken by our general constitutive equa-

nonsingular changes of local reference configuration tions when the material under consideration is a fluid.

that leave the response functions of the material un- We say that a material is a fluid if its symmetry

altered.39

If we assume that the internal state variables are

quantities unaffected by the choice of reference con-

a. group S is the group 'U of all unimodular tensors. The

property of being a fluid is intrinsic to the material

in the sense that S='U for one reference configuration

figuration, then in our present theory the symmetry only if S='U for all reference configurations. Assuming

group S may be identified with the group of all m- that the internal state variables a, obey the "scalar

vertible tensors H for which the identities transformation rule" (12.2) under changes of frame,

$(F, 8, a) =$(FH, 8, a), and using arguments now familiar in continuum

mechanics, one can easily show that for a fluid the

n(F, 8, a) =~(FH, 8, a), following representation formulas must hold for the re-

T(F,8, a) =T(FH, 8, a), sponse functions occurring in the identities (12.3) and

(13.1) :

q(F, 8, g, a) =q(FH, 8, g, a),

(13.3)

f(F, 8, g, a) =f(FH, 8, g, a), (13.1)

(13.4)

hold for all F, 8, a, and g. This group S depends on

the choice of reference configuration, but the sym- T=-pl, p=p(u,8, a), ( 13.5)

metry group corresponding to two different reference q=-Kg, K=R(u,8,g, a), ( 13.6)

configurations of the same material are conjugate and

hence isomorphic. A theorem of Gurtin and Williams40 ci=f(v, 0, g, a). (13.7)

tells us that the postulate of positive production of

entropy requires that S must be a subgroup of the uni- Here u = 1/p is the specific volume; g= (g. g) 1/2 is the

modular group; i.e., that each H in S must have magnitude of gradO; $, n, p, R, and the components

I detH 1=1. ji of f are all scalar-valued response functions; p

The similarity between the equations (13.1) and the and K are called, respectively, the pressure and the

identities used to define the symmetry group of an thermal conductivity. It follows from (13.3)-(13.5) that

elastic material with heat conduction is striking,41 and for fluids the entropy relation (5.16) and the stress

one can immediately apply here many results originally relation (5.17) become

obtained within the framework of the theory of elastic

TI=-a8~(V, 0, a),

materials. For example, using an argument given by

Coleman and Nollia one can easily show that if the (13.8)

inversion transformation -1 is in S then

When it is more convenient to take the specific entropy

q(F, 8, 0, a) =0 (13.2) of the fluid, rather than the temperature, as an inde-

for all F, 8, and a. Thus, even if (F, 8, a) is not an pendent variable, we have

equilibrium state, the presence of -1 in S implies =E(V, TI, a),

that the heat flux q vanishes when grad8 vanishes.

We do not discuss here the symmetry groups ap- O=O(u, TI, a) =a~E(U, TI, a),

propriate to the various types of solids. The interested

reader will have little difficulty in extending to our p=p(u, TI, a) = -avE(U, TI, a), (13.9)

present subject the known theory of symmetry in finite

and when the specific internal energy is the preferred

elastic deformations.42 However, since the theory of

independent variable

39 This is essentially a definition due to Noll3s who defined the

local isotropy group 9 of a material to be the set of density-pre- TI=71(u, , a),

serving changes of local reference configuration which leave the

response unaltered. It has recently been shown40 that our present 8= B( u, , a) = [a.71 ( u, , a)]-I,

S must reduce to Noll's g.

40 M. E. Gurtin and W. O. Williams, Arch. Rational Mech. p=p(v, , a) =oav71(v, , a). (13.10)

Analysis 23, 163 (1966).

41 See, for example, Ref. 13, Eq. (3.7). It is clear that for fluids all the remarks we made

42 For some pertinent results in that theory see the articles of

Smith and Rivlin43 and Coleman and Noll.44 about stability in Secs. 6-10, remain valid if the modi-

43 G. F. Smith and R. S. Rivlin, Trans. Am. Math. Soc. 88, fier "at constant strain" is replaced by "at constant

175 (1958). volume"; i.e., if the condition that F be constant is

4' B. D. Coleman and W. Noll, Arch. Rational Mech. Analysis

15, 87 (1964). replaced by the weaker condition that u be constant.

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612 R. D. COLEMAN AND M. E. GURTIX

that each ai transforms as a scalar upon changes of (14.3)

frame, for a fluid the stress is always a hydrostatic

pressure. This observation, when combined with the a is called the vibrational energy, fA is called the active-

comments made at the end of Sec. 12, suggests that mode energy,46 the value '1v of ;jv is called the vibrational

the present theory lacks the breadth of applications entropy, and the value '1A of ;jA is called the active-mode

enjoyed by the theory of the thermodynamics of entropy. The number

materials with fading memory. I.; In that theory a fluid ( 14.4)

out of equilibrium can exhibit shearing stresses. It

should not, however, be concluded that the present IS the translational (or active-mode) temperature, while

theory is a trivial special case of the theory of Ref. 15. (14.5)

Three reasons for this are the following: (a) The ma-

terials we consider here need not obey the principle of is the vibrational temperature. We now add the usual

fading memory; in fact, that principle follows from assumption that a obeysA a scalar differential equation

our present assumptions only after the addition of very of the type (13.7) with f independent of g and linear

strong stability assumptions for the differential equa-

tion (4.5). (b) Since g appears in (4.5), for the ma- a=A (v, e) -B(v, (J)a. (14.6)

terials we consider here the past history of g may in- If we assume that the temperature e obeys a con-

fluence the stress. (c) Those special materials which stitutive equation of the form e= o( v, f, a), then the

are covered by both the present theory and the fading present theory based on the constitutive relations

memory theory can be described in the present theory (14.1)-(14.3) and (14.6) clearly falls as a special case

with a mathematical language that is somewhat of the theory of fluids obeying (13.3)-(13.10). (Of

simpler and which, at the present time, appears closer course, here the internal-state vector 0: has just the

to kinetic-theory interpretations (a good example of one component a.) We may therefore conclude from

such a special case is given in our concluding section). (13.1Oh.3, (14.2), (14.3), and (14.4) that

It is clear that by adding F to the set (F, (J, g, 0:) of

independent variables used in (4.1) -( 4.5), one can p=eOv;jA(V, fA), (14.7)

generalize our present development so as to obtain a

(J=eA. (14.8)

theory in which fluids exhibit shearing stresses and in

which 0: can be a string of tensors of arbitrary tensorial Thus in this theory "the temperature" (J must be identi-

rank under changes of frame. 45 However, such a theory, fied with the translational temperature eA. This fact

since it would mix two distinct but specialized concepts has already been established in a much more general

of internal dissipation, would lack both the simplicity context; indeed, (14.8) is an immediate consequence of

of the present theory and the breadth of the general the remark containing (11.7). We may conclude from

theory of materials with fading memory. the theorem following (11.9) that in a stable equilib-

rium state the vibrational temperature ev is equal to

14. IDEAL GASES WITH VffiRATIONAL

RELAXATION the translational temperature e.

Noting that (14.1) and (14.7) imply the partial

We here illustrate our theory with a simple special differential equation

case: a dilute nondissociating diatomic gas which, al-

though it does not conduct heat and obeys the ideal gas (14.9)

law in the form

pv=R(J, (14.1) 46 Or, at length, "the specific internal energy of the active

mode."

with R a constant, can, nonetheless, exhibit dissipa- 47 This hypothesis, which differs only slightly from a postulate

tive phenomena due to the finite time required for the studied by Herzfeld and RicelO in 1928, has been discussed by

Rutgers,48 Kneser,9 Landau and Teller,60 Bethe and Teller,a

transfer of molecular motion from the translational Rubin and Shuler,61 Montroll and Shuler,"' and others. The studies

mode, where it contributes to the pressure, to the of Rubin and Shuler6 ] and Montroll and Shuler62 indicate that

since (14.6) holds precisely for a harmonic-oscillator model, it

vibrational mode, where it does not. To place this should hold near to equilibrium for more general models. See

familiar theory in our present framework, we first also Ref. 53.

assume that the entropy of the gas can be written in '8 A. J. Rutgers, Ann. Physik 16, 350 (1933).

'9 H. O. Kneser, Ann. Physik 16,360 (1933).

the form 60 L. Landau and E. Teller, Physik. Z. Sowjetunion 10, 34

(1936).

(14.2) 61 R. J. Rubin and K. E. Shuler, J. Chern. Phys. 25,59 (1956).

62 E. W. Montroll and K. E. Shuler, J. Chern. Phys. 26, 454

46 A simple and particularly elegant special case of a fluid of (1956).

this type, with the internal-state vector a transforming as a 63 W. G. Vincenti and C. H. Kruger, Introduction to Classical

spatial position vector, has been studied by J. L. Ericksen, Kol- Gas Dynamics (John Wiley & Sons, Inc., New York, 1965).

loid-Z. 173, 117 (1960). Chap. 7.

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65.30.29.111 On: Sun, 16 Mar 2014 01:05:33

THE R MOD Y N A M I C S WIT H I K T E R K AL S TAT E V A R I "\ B L E S 613

we see that iiA must have the special form Let us now assume that for each a and v we can

find a 0 such that a=/(v, 0). It is then a direct conse-

1]A =R Inv+h(EA). (14.10) quence of the theorem following (11.16) that for each

Assuming that h is smoothly invertible, we can write fixed v the function Ov defined in (14.5) is the inverse

(14.10) in the form of the function I( v, .). Hence I( v, 0) must be inde-

pendent of v,

EA=WA(V exp( -1]A/R)

I( v, 0) = 1(0), ( 14.16)

=WA(V exp{[iiv(a) -1]J/R}) and

(14.17)

=~(v, 1], a) -a. (14.11)

with the function 1-1 the inverse of I.

It follows from (13.9h and (14.11) that Equations (14.3), (14.13), (14.15), and (14.16)

0= -R-1WA ' (v exp( -1]A/R)v exp( -1]A/R) (14.12) imply that the value E* of the specific internal energy

of the gas when it is in equilibrium with temperature

with the prime indicating the derivative; hence 0 is a 0* and specific volume v* is independent of v*; in fact,

function of only vexp( -1]A/R). Assuming that this

function is invertible, we may solve (14.12) for e* = fA (0*) +/(0*). (14.18)54

v exp( -1]A/R) in terms of 0 and write (14.11) in the In view of (14.16), we can write (14.14) in the form

form

( 14.13) a=k(v, 0)[/(0)-0'], (14.19)

where

Thus, the active-mode energy is here a function of the k(v, 0) >0, 1(00. (14.20)

translational temperature alone.

We now add the natural assumptions that a is ACKNOWLEDGMENTS

always positive and that the differential equation (14.6)

obeys the stability postulate discussed in Sec. 10. We thank J. Kestin, J. Meixner, and B. H. S. Rarity

These assumptions imply that (14.6) can be written for stimulating discussions about thermodynamical

in the form systems with internal degrees of freedom. This re-

( 14.14) search was supported in part by the U. S. Air Force

a=k(v, 0) (/(v, 0) -a),

Office of Scientific Research under Grant AF-AFOSR

with the functions k and I positive. Furthermore, the 728-66 and by the Office of Naval Research under

function I in (14.14) here plays the role of the equilib- Contract Nonr-51031.

rium response function a* in (6.17): For each pair 54 Since the equilibrium pressure p* is just R()* /v*, to prove

(v*, 0*) the vibrational energy 0'* given by .*

that is a function of ()* alone we could have used an argument

similar to that giving us (14.13). In this instance the proof would

( 14.15) proceed exactly as it does for an ideal gas without relaxation

a*=/(v*, 0*) effects, in which context the proof is spelled out in detail by R.

Courant and K. O. Friedrichs, Supersonic Flow and Shock Waves

makes (v*, 0*, 0'*) an equilibrium state. (Interscience Publishers, Inc., New York, 1948), pp. 8, 9.

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