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1961 J. Nucl. Energy, Part C Plasma Phys. 2 188

(http://iopscience.iop.org/0368-3281/2/1/330)

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J . Nucl. Energy. Parr C : Plasma Physics, 1961, Vol. 2. pp, 188 1 0 193. Pcrgamon Press Lrd. Printed in Norrhern Ireland

NON-EQUILIBRIUM THERMODYNAMICS OF SYSTEMS IN

AN ELECTROMAGNETIC FIELD
s. R. DE GROOT
Lorentz Institute, University of Leyden, Leyden, Netherlands

Abstract-A review is given of some applications of thermodynamics of irreversible processes to systems in

the presence of an electromagnetic field. The conservation laws of mass, niomentuni and energy and the
entropy balance equation are developed for mixtures without and with electric and magnetic polarization.
and also for systems in which the momentum transfer between some of their components is inhibited.

1. 1 N T R O D U C T I O N theory of such a system rests on a more hypothetical

MACROSCOPIC theory of irreversible processes can deal basis than the theory of ordinary mixtures. One of
with a number of problems concerning irreversible the results is that a relaxation phenonienon of scalar
processes in systems of which some components carry heat flow between the components may arise. I t is
electrical charges. In the framework of thermo- studied how this ecect is coupled with n chemical
dynamics of irreversible processes the conservation reaction in the system.
laws of mass, momentum and energy are set up for 2. S Y S T E M S I N A N E L E C T R O M A G N E T I C
systems of which the properties are continuous func- FIELD (WITHOUT POLARIZATION)
tions of tinie and space co-ordinates. Then the en- Let us consider a mixture of / I components and
tropy law is written down and with the help of the write down the conservation laws of mass, momentum
conservation laws an entropy balance equation is and energy as well as the entropy law and entropy
derived which contains a source term, the entropy balance equation.
production, which characterizes the irreversibility. ( a ) C o / i s e r r a t i o / z of 117ass is expressed by
This source term contains the fluxes and thermo-
dynamic forces which are used in the description of - _ - -div pIcv,,. ( k = I , 2, . . . , I I ) (I)
irreversible behaviour (PRIGOCINE, 1947 : DE GROOT, at
1951 ; D E GROOTand MAZUR,to be published). where p k is the density of coniponent h-. and v k its
In the present review three particular cases are velocity. We shall suppose i n this section that no
considered. In the first place (Section 2 ) systems are chemical reaction occurs; otherwise at the right-hand
studied which consist of a mixture of chemical com- side of (1) one term more would arise, describing the
ponents, some of which carry electrical charges, but production of substance k by chemical reactions (cf.
which are not supposed to be polarized by the electro- liowever Section 4). An alternative form of ( I ) is
magnetic field. I n such systems heat conduction,
diffusion, electric conduction, viscous flow and a
number of cross-phenomena between these effects can
take place. The thermodynamic theory of many of
these effects has been developed. I n the second place
and ,<
where cl2= p k / p (with p = Xlcpl<)is mass fraction of

(Section 3) it is investigated how the scheme must be J, == pk(vI,,- V) (k 1, 2 , . . ., / I ) (3)

anlplified if we also consider electric and i n a p e t i c represents the diffusion flow of k . The velocity v is
polarization phenomena to be present i n the system. the centre of gravity velocity defined by PV ==
We then have, besides the aforen1entioned effects, C,p,V,. The time derivative in (2) is the barycentric
also electric and magnetic relaxation phenomena. substantial derivative a!at - V grad.
Another problem concerning polarizable systelns ( 6 ) C O / ? S e ~ Z I 7 t i O / lO/ 1170/7?E/ltl/llI. From Maxwells
which can be treated in the framework of the tlieory eqUatiOnS for SyStelnS without electric and magnetic
is the question of pressure and ponderolnotive force, polarization (E == D. H = B) one can derive a bal-
which notions may be defined in different ways. ance equation O f electromagnetic molllentUm O f the
Finally a third case (Section 4) is considered in which following form
the transfer of momentum between some of the com- -
ag - - Div T - F, (4)
ponents of the system is hampered. The macroscopic at
188
 Noli-equilibriLim thcrmodynnmics of systems in an clectromngnetic field 189

\\.litre g is the electromagnetic momentum density, T the density of electromagnetic energy e,, the flow of
the Max\\ell tensor of electromagnetic stresses and electromagnetic energy (Poynting vector) S and a
- F a source of momentum. These quantities are source term U,. These quantities are given by
given b\.
c
pi = 1 E2 1
.__ B'
I 2 I " , (16)
g--EXX. (5) S == CEX B,
C (17)
T == EE .;. BR .- b(E' ... B?)):, (6) 0,= I * E. (18)
1 Conservation of total energy can be expressed by
1; = p z E - I xB. (7)
C
ape-- -div J,,,
-
Here E and B are the electric and magnetic field, U at
the u n i t tensor. z the charge per u n i t mass (defined where e is the total energy per unit mass and J, the
by - p '. - with the charge of k per u n i t mass)
-/,-,J+
7::
total energy flux. Let us now define the internal
and I thc electrical current (Xk-pii:avk). energy LI and the heat flow J, by splitting the two
Consen.ation of total n~onientumcan be expressed quantities which occur in (19) in the following way
as
a
-(pv -- - g) =: -- Div ( p v v -L P - T ) , (8)
pe = $.pi.? ., Lef + pic, (20)
at J,. = J k i n f S + P U V -tJ,. (21)
where P is the pressure tensor (it is actually defined I f one now subtracts the balances (11) for jpc.' and
by this equation). When (4) is subtracted from (8) ( 1 5) for e, from (19) one obtains the balance equation
one obtains (using also the barycentric time derivative) of internal energy
nv dU
P -d=t - Div P 1F. (9) p- = -di v J , , - P : G r a d v f i *
nr
the equation of motion, with the Lorentz force density (22)
F as a source of momentunl. Clearly one can also
Splitting the pressure tensor into a n equilibrium part
write for (7)
1
pU and a viscous pressure tensor rI,and denoting the
F = XI,.pkF,., F, = =,<(E- - V B X B), (10) electric field measured by an observer with a velocity
C
+
v as E'(= E (vir) X B) one can write instead of
where F, represents a force per unit mass on coin- (22)
pone tit k .
dU dp-1
(c) Coriserratiori of'mergjq. Let u s first establish a p- = -di v J,, - p p -- I1 : Grad v -,- i * E.'
balance equation for the kinetic energy, which follows dt dr
from multiplication of (9) by v : (23)
a form of the first law of thermodynamics.
( d ) The eritropj. h i t , (Gibbs' relation) has the form
\diere
Jhll,= $p[.'~ -- P Y, - (12)

'ThlIl = P : Grad v - p ~ *v E -i ' (f V X (13) where s is the entropy per unit mass and pk the ehemi-
cal potential of component k. This law is valid along
and hit11
i = v the barycentric motion if deviations from equilibrium
- v)
"I,p/,-h(v/, = 1 - pzv, (14) are not exceedingly large (PRIGOGINE,1947; DE
M.hicIi IS the conduction current. GROOT, 1951; DE GROOTand MAZLIR,to be pub-
Another equation can be deduced from Maxwell's lished).
equations : ( e ) The eritrop~.halarice equatiorl is obtained from
(24) with the help of (2) and (23):
-?el_ -
- -div S -
at
aPs -
- - -div J,*4- U ,
the balance equation of electromagnetic energy. with at
190 S. R. DE GROOT

where J, is the entropy flux and U the entropy pro- where p = p-P and m = p-lM are the electric and
duction, are given by magnetic polarization per unit mass. Furthermore
I1
conservation of total momentum is again expressed
J,5 = PSV - (J, - 2
k=l
pkJ,)/T, (26) by (81, a n d the equation of motion is (9). The force
T o = - - J1J , . g r a d T -
1L
J , * T g r a dPL F contains the Lorentz terms encountered already i n
T k=1 T Section 1, and moreover terms involving the polari-
-
- i E - I7 : G r a d v 2 0.
(27)
zations. The latter are called together the pondero-
motive force. The tensor T and the vector F could
The latter quantity is positive definite according to b e defined differently since only Div T - F and P -- T
the second law of thermodynamics and measures the (cf. equations (4) and (8)) are well-defined quantities.
irreversibility (it vanishes at equilibrium). It consists Tlie form adopted here fits well into the thermodyna-
of a sum of products of so-called fluxes and thermo- mical description and is moreover essentially the
dynamic forces. It is seen to contain terms arising ponderomotive force proposed by Kelvin. We shall
from heat conduction, diffusion, electric conduction later show that the more familiar different form.
a n d viscous flow respectively. In non-equilibrium proposed by Helmholtz, is not contradictory witli
thermodynamics one establishes linear relations be- Kelvins expression.
tween these fluxes and thermodynamic forces, and (iii) Conserration of energy. The balance equation
one studies the properties of the so-called phenomeno- (11) of kinetic energy is again obtained by m u l t i -
logical coefficients which occur in these linear relations, plication of (9) by v. After some manipulation one
The scheme of these coefficients can be simplified as finds
a result of possible spatial symmetries of the system Jkin = &pr2v - P * v - (P * E -- M * B ) V.
(Curies principle) or as a result of time reversal
invariance of the equations governing the motion of
the individual constituent particles which leads to the gki,,= P : Grad v A- -
pzv E - i * (f. Bl
Onsager reciprocal relations.
In such a way one can study various phenomena
- P E . - -dp .
B __
dm - E - -ap
dt (It ai
such as electric conduction, thermo-electric pheno-
aB
mena, thermomagnetic and galvanomagnetic effects, I( Mx f) - aaE
r-B*- aatw - ( P X ;)v *-
at
and the like (PRIGOGINE, 1947; DE GROOT,1951 ;
DE GROOT and MAZUR,to be published). (31)
where the primed quantities
3. P O L A R I Z A B L E S Y S T E M S I N A N
ELECTROMAGNETIC FIELD E = E - - v1 X B , B = B - - v1 X E. (32)
The formalism of the preceding section must be C C

modified if the system can be polarized by the electro- I 1

magnetic field. We give here a summary of the results P=P+-MX v , M=%l--Px v (33)
C C
for this case.
(i) Conseroation of mass is still expressed by ( I ) are the fields and polarizations as nieasured by an
o r (2). observer with velocity v.
(ii) Consercation of momentum. A balance equa- The balance equation of electromagnetic energy ( 15)
tion (4) of electromagnetic momentum can be derived can again be obtained from Maxwells equation. ~ i t h
from Maxwells equations, but now with the following the following quantities
expressions for the quantities occurring in it V
e, = :E2-1- $ B 2 - M B - - * (E X NI). (34)
C

S = CEx H, (35)
V
T=DE+-BH+-(PX B - M X E)
C
- ( t E 27 i B 2 - M * B)U, (29)
F =pzE + 1
-I
C
x B + (Grad E) - P
+ (Grad B) - M + --P -
d
dt
(p x
r -*.
B - m X E),
Conservation of total energy is given by (19).
(30) Again by using the decompositions (20) and (21) one
 Non-equilibrium thermodynamics of systems in an electromagnetic field 19 1

gets after subtraction of ( I I ) and ( 1 5 ) from (19) the which is the generalization of Gibbs' relation for
balance equation of internal energy polarized systems, valid along the centre of gravity
motion. It must be noticed that E a n d B in (44) are
p
tlll
-
'lt
= -div J,) - P : Grad v + i - E' the equilibrium fields.
(v) The entropy balance equatiori ( 2 5 ) follows from
(44) after inserting (2) and (37), with the entropy flux
(26) and the entropy production CT given by
- - TI : Grad v f i - E'
dp-1
- pp 71

dt Ta = -J,, . -T'I grad T - Tk2- 1 J,; P

grad -E
T
-+ i E'

(37)
dt '
AB' ")dt ,
- II : Grad v.
tlie form of the first law of thermodynamics for
polarized systems. (45)
( I L ) The elitropy Ian,. I n order to establish the second As compared with (27) this formula contains two
lab for polarized systems, let us first consider a one- additional terms describing electric and magnetic
component polarizable system at rest and confined relaxation. The quantities AE' and AB' are the devi-
to a constant volume V with surface (2. Energy ations of the values of the fields, which occur in
conser\ ation is then expressed by ( 3 7 ) , from their equilibrium values which occur in
(44).
d E = dQ ~ dwen1,
t ~ w n l c c iT (38) (vi) Onpressure andpoideromotireforce. As remarked
wlirre E is the total energy, d Q the heat added and before, pressure and force can be defined in different
dWn,,,h and dW,, the mechanical and the electro- ways in polarizable systems (MAZURand PRIGOGINE,
magnetic work performed on the system in a time dt. 1953; MAZURand DE GROOT,1956). We encoun-
One has tered a pressure p and a ponderomotive force F, which

y s LfSZ = - J'.div S dV
was essentially the Kelvin force. One can, however,
define the pressure in a different way and thus obtain
a corresponding different force. In particular the
pressure in a polarized state of the system is some-
times defined as the pressurep, measured in the system
Inserting this and also (20) with (34) for our system, at equilibrium when one reduces the fields to zero,
which is at rest ( v = 0), into (38) yields but keeps temperature and density constant. In order

tlC' -= (IQ -!- cIW,,,,,~, A

s I-
(E * dP - B * AM) dV.
(40 1
to find the relation between p o and the pressure p
introduced before, let us introduce the Helmholtz
function
f=u-Ts. (46)
For ii reversible transformation one has therefore
With the help of the Gibbs' relation for polarized
t/L' ~- + S
TtlS -:- dW,~,'~?~,l, ( E t f P
' I
-- B * dM) clV,
(41)
systems, one has then
a=
' -sdT - pdr +E * d -
~ B - elm,
~ (47)
froin \vliich we can conclude, since the density is where 1' = p-' is the specific volume. The polariza-
cons til nt. tions are related to the fields by means of the linear
relationships
(/U = T 61s --!- +
cli~~;$;>~,,, E dp - B * elm. (42) pp = P = K E , (48)
One can convince oneself easily that the deformation
parameter of tlie mechanical work is only the density
mp = M = ZH = (x/(x - 1)}B, (49 )
so that (42) becomes where K and are the electric and magnetic suscepti-
bilities, which are scalar quantities in isotropic systems
T d s = tlu + p clp-I - E dp - - B elm. (43) (the case which we shall study here). Integrating (47)
For an open system this can be generalized to at constant temperature and density, one obtains with
T d s = du 7-p dp-1 - E clp - - B r/m - dct, (48) a n d (49)
(44) , {(/CL')-'p' -;- &(XL')-'(x
, f = j 'I1 -:- l)t7i2, (50)
192 S. R. DE GROOT
where fois the free energy a t temperature T, density
p = r-l a n d fields zero. Differentiating this relation
with respect to the specific volume, at constant
temperature and polarizations, gives
the connexion between p and po which we wished to
derive.
I n the equation of motion occurred the expression
grad p-F. Should we prefer to use p O instead of p ,
then we must introduce also a different force F,
such that
grad p - F = grad po - Fir. (52)
This equality gives with (51) and (30) for the
equilibrium case
F,, = ,dE + -C1 I % B - _:E2grad IC
(53)
the so-called Helmholtz ponderoniotive force, which
is seen here to correspond to the use of as pressure.
(vii) Relafiristic theory. The preceding considerations
were all non-relativistic. It may, however, be remarked
that a fully relativistic theory exists, of which the non-
relativistic approximation is identical to the formalism
summarized above (KLUITENBERG, D E GROOT and
MAZUR,1953; KLUITENBERCand D E GROOT, 1954
and 1955).
4. T W O - F L U I D T H E O R Y
It has been suggested that the macroscopic equations
which describe the behaviour of a mixture may have
to be fundamentally altered if the transfer of momen-
tum between some components of the mixture is, for
some reason or other, inhibited (PRIGOCINE and
MAZUR,1951; MAZURand PRIGOGINE, 1951). In
such a case these parts of the system are sometimes
referred to as fluids. This inhibition hypothesis is
then supposed to have as a consequence that separate
Gibbs relations must be written down for the various
fluids since approximate statistical equilibrium is no
longer established around the centre of gravity motion
of the mixture but only around the macroscopic
velocity of each fluid separately:
(54)
In this equation x numbers the fluids, which may each
consist of a number of chemical components n u n i -
bered by the index i. (The time derivative must be
counted with respect to the average motion of fluid
x . ) The existence of different temperatures T, for the
various fluids y. leads to the possibility of a scalar heat
flow between the fluids. We shall i n the following
study a system which we shall for convenience suppose
to be at rest, but in which we allow, in contrast with
the preceding sections, a chemical reaction to take
place between the various components, which d o not
all belong to the same fluid. This case is interesting
since because both the relaxation phenomenon referred
to in Section 1 (scalar flow of heat) and the chemical
reaction are scalar processes they can couple even i n
isotropic systems, thus giving rise to interference
phenomena. Let us develop the theory of such a
system by writing down the conservation and entropy
laws.
( a ) Couserrntioii of mzss. We can write for the mass
equation
where p x i is the density of component i of fluid X .
At the right-hand side no divergence of a flow appears,
since the system was supposed to be at rest. However,
a source term vXiJrarises, which describes the pro-
duction of matter of the species x i by the chemical
reaction. The quantity v X i divided by the molecular
mass M Z i of xi is proportional to the stoichiometric
coefficient of y.i i n the reactional equation (these
quantities are counted positive if the substance xi
appears there at the right-hand side, negative if it
appears at the left-hand side). The factor J,. is called
the chemical reaction rate. Conservation of mass can
be expressed as
& t v x i = 0, (56)
because the left-hand side of (55) summed o\er Y. and
i vanishes i n a system at rest (constant density p ) .
( 6 ) Conserratintz of energy is expressed by
(57)
For a system with electromagnetic forces ( b u t no
po 1a ri za t i o n ) o r wit 1 co n ser va t i ve ex t tr 11a I forces
(such that the potential energy is conserved i n thc
chemical reaction). this equation leads to an internal
energy balance equation for fluid x of the form
 Non-eqtiilibriun~thermodynamics of systems in an electromagnetic field 193

where the source terms y x satisfy with the Onsager relation

( c ) The eurropy laii. (54) becomes for a system at rest
( d ) The entropy balu~iceequcrtio/7 is obtained by in-
serting (55) a n d (58) into (60). This yields
where 6, is the entropy production in fluid x , given by
T h e phenonienological coefficient L,,,, describes the
scalar heat conduction, L,, the chemical reaction
velocity a n d L,,, a n d L,,, characterize mutual inter-
ference phenomena between the relaxation process
and the chemical reaction.
If the chemical reaction takes place at a much
quicker rate than the energy flow. a kind o f stationary
state would be reached in which the reaction rate J ,
would vanish. Then from (70) we have

Let us compare this quantity, which gives the thermo-

where we have explicitly indicated that p X tis a function dynamic chemical force X , per unit temperature force
of t h e temperature T,. A', in the state of vanishing chemical reaction rate,
The total entropy production for a two-fluid system with another quantity which characterizes another
( 2 = I , 2 ) is then, using also (59), and the notation important physical situation, namely the state of equal
J , , for y1 = -Y2, temperature (Xi' = 0). Then o n e has from (69) and
(70)
- L,,c
- - (73)
L,, '
here
A,(T,) = SLp,f(T,)~,t. (2 = 12) (64) This quantity, which we shall abbreviate as U * , is
therefore t h e energy transfer per unit reaction rate a t
We can write (63) as a sun1 of products of fluxesJ,,
the isothermal state. Both quantities (72) a n d (73)
and J , a n d thermodynamic forces A',,and X,.
could in principle be measured and it could be checked
(5 = J,, X , , -- J , X,, (65) whether the Onsager relation (71) which with (72)
where a n d (73) can be expressed as

and
is experimentally verified.
PKIGOGIKE a n d GEHENIAU (1946) have sludied t h e
example of a gas plasma, where the chemical reaction
is t h e ionization of a molecule A into a n ion I and a n
electron e :
(67) A -'I
c -- P . (75)
The fluid x = I consists of the molecules A a n d t h e
with the symbol Aq standing for the difference of a ions I with temperature T I a n d molecular masses i t l
quantity with index 2 a n d the same quantity with and M - 177, the fluid 2 consists of the electrons with
index I . The quantity A is the so-called chemical teniperature T, and mass 117. The stoichiometric
affinity coefficients of reaction (75) for m o l e c ~ ~ l e sions
. and
A = x,,ip,Lv,; (68) electrons are clearly - I . - . 1 and -. I respectivcly, a n d
of the reaction. the quantities can therefore be chosen a s - I .
The linear plienomenolo~ic31relations for the fluxes 1 - M/m a n d ,M//il respectiLely. The plasma is
and forces of (65) are supposed to be i n such ;I statc that the degree of
ionization is approximately t h e sanw M liicli would
J , , = L , , , , X , , l- L,,,.X,, ( 6 9 ) exist ;it eqtiilibrium. i.e. a t il temperature between T,
J,. = L,.,,X,' L<,rx(, (70) and T,. Furthermore. sincc the heot contcnt of the
I ::
194 S . R. DE GROOT

first fluid consisting of the heavy particles is much it follows with (79), (80) and (81) that
ereater that the heat content of the second fluid, we
c
A'- KO AT
may consider TI as practically the temperature of -=
chemical equilibrium. This means that the chemical KO
affinity A is zero for the temperature TI and (67) be- 11,111 - u * M - kT
comes thus = 2 ( kT (84)

which gives the relative deviation of the chemical rate

constant from its equilibrium value.
I f in the preceding derivation polarizable media
because A , contains only quantities referring to tlie would have been studied. one would have found i n
second fluid, which consists of the electrons e. The the entropy sourcc strength terms related to electric
last expression can be written as and magnetic relaxation besides the relaxation term
and the cheniical term appearing i n (63).
(77) Finally it inay be noted that in two-fluid systems,
which are not at rest, PRIGOGIKE and M A Z U R(1951)
with 11, the partial specific enthalpy, r,, the partial have found that a characteristic 'friction term' arises
specific volume a n d P , ~the partial pressure of the i n the entropy source strength, which depends on the
electrons. The Onsager relation (74) becomes with relative velocity of the two fluids, and which is absent
(66) and (77) i n the case of ordinary mixtures. On the other hand
/7,111
~ $ 7 ~ - U"M i n two-fluid mixtures terms, arising from diffusion of
- -- (78) che iiiical components be 1on gi 11g to different fluids
AT P<,ITIT '
with respect to each other. are missing from the en-
v,hich, with the perfect gas law p,,r = kT//17,becomes tropy production. Such terms arise only in ordinary
LIP,, / i , , i j i - ti*' M AT mixtures, wli ere the transfer of moment u in bet ween
- -- (79)
PC kT T ' all chemical coniponcnts is uninhibited.
giving the deviation of the electron pressure from its REFERENCES
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verification of (79) the quantities Ap,./AT at zero North Holland Publishing Company: Anistcrdani. Inter-
reaction rate J, == 0 and tlie 'energy of transfer' if* science Publishcrs, New York.
at the isothermal state should be measured. Gne can GROOTS . R . DE and MAZER P.. ~ f l i / - c , ( / / i i / i i ~ i . i / i i iTlwrii~o-/
t/jrrai?rics.North I-lolland Publishing Company. Amsterdam.
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A i i i s f c , r t / f / / i r 20, 199; (1955) 21, 148. 169.
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i c / r l c~./ / l ; / l O / l / C ~ i / C/l'J'c;t'cl'-
~.\
s i l k s , Desoer, Liege.
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661.