Theoretical Investigation of V A P O U R Transfer Through A Capillary-Porous Body
Theoretical Investigation of V A P O U R Transfer Through A Capillary-Porous Body
Theoretical Investigation of V A P O U R Transfer Through A Capillary-Porous Body
Abstract--In the first part of the paper an investigation is made of the capillary evaporation under
free molecular conditions for a nonisothermal case with assumption made of the evaporation occurring
both on a lateral surface and at the bottom. Two modes of reflection from the surface, diffuse and
specular, are considered. In both cases approximate expressions are derived for the fluxes of molecules
at the capillary exit. In the case of diffuse reflection, the flow of molecules leaving the unit lateral
surface and the net surface flow are obtained as well. This expression allowed investigation of the phase
transition at the wall depending on the dimensionless length and temperature drop.
In the second part it is shown that the effect of surface diffusion on the capillary conductivity is
determined by the dimensionless parameter GL equal to the squared ratio of the square mean displace-
ment of a molecule over the surface to the capillary length, and preceding the senior derivative in the
initial integro-differential equation.
In the third part, based on the approximate theory of the mean free molecular path length, an
expression is found for a vapour flow through a high-dispersed porous body when the capillary model
is an inexact one.
More grounded calculations of vapour transfer in and condensation processes in the capillary. This
capillaries with evaporation are presented, for example phenomena is observed only at nonisothermal condi-
in [2], where the account is taken of a thermal slip tions and may be referred to as the thermal effect of
in the presence of a temperature drop along the vaporous moisture migration.
capillary wall as well as of diffusional (diffusional drift) Successive condensation and evaporation in a pore
and viscous slip. The values of these effects are found or capillary over liquid menisci were discussed earlier
to be comparable with the Stefan flow. as well but these processes were considered to pro-
The account taken of film motion of liqueous ceed at isothermal conditions. In the authors' case
moisture over capillary walls contributes to further moisture evaporation and condensation in capillary
improvement of the model mechanism of capillary are determined by the temperature drop along its
transfer [3]. Film motion of moisture is caused by the length and by the geometry of pores and capillaries
difference of liquid chemical potentials near the of the body. This is the principle point in the mechanism
capillary wall and in the bulk of liquid. It is the of moisture transfer in the capillary under the authors'
difference of chemical potentials which creates the consideration.
so-called wedging pressure. The wedging pressure is It was found through a number of investigations
determined by the pressure difference between the that surface diffusion of vapour or gas contributes
liquid-solid phase on a flat interface between the liquid much to the transfer process. Therefore the velocity
in a thin layer and the bulk of liquid adjacent to of vapour migration along the capillary length depends
the thin layer. Thus liquid evaporation proceeds not not only on the linear diffusion velocity but also on
only on the liquid meniscus in a capillary but also the time of molecule adsorption on the surface of the
from capillary walls covered with a thin liquid layer. capillary wall, i.e. on the velocity of surface diffusion.
Up to now, however, no kinetic consideration has Such a vapour migration mechanism is discussed in
been given to surface evaporation of a thin liquid layer the second part of the paper. The relationships obtained
covering the capillary walls. may be used to analyse the mechanism of drying moist
In the paper an attempt is made to describe in materials and transpiration cooling of heat-protecting
detail the mechanism of vapour transfer with a free- materials.
molecular flow in a thin capillary (microcapillary) To conclude, itis shown how the approximate theory
with account taken of evaporation both from the liquid of the mean free path length may be used for investi-
meniscus and from the lateral side of the capillary in gation of the kinetics of vapour transfer through a
the presence of a temperature gradient along the highly disperse porous body when the capillary model
capillary wall. The analysis of such a mechanism has is inexact.
shown that inside a capillary-porous body partially
filled with liquid the evaporation and condensation
processes may occur. The dimensionless parameters
s and / are the main characteristic values. The first is I. MICROCAP1LLARYVAPOUR FLOW INCLUDING
a product of the dimensionless heat of liquid-vapour PHASE CONVERSIONS
phase transition and relative temperature drop along We shall consider a cylindrical capillary with a fiat
the capillary, and the second is the capillary length to bottom (X = 0) from one side, and evaporation (sub-
radius ratio (dimensionless length of the capillary). limation) proceeding both on the lateral surface and
Rough estimation of s for liquid evaporation.into at the bottom. A constant temperature gradient is
vacuum (To = 220°; T = 10"C) yields s -~ 1.3. Then for prescribed along the capillary. The number of mol-
l = s and at / > 1 (i.e. when the capillary length is ecules evaporating from the unit surface per unit time is
greater than the radius), vapour condensation may
occur at the capillary meniscus, while near the exit Pe(T)
evaporation may proceed. However, if I < 1 (the length j(o:, T) = ~ (2~mk r)l/2 .
of the capillary is less than its radius) evaporation
takes place at both capillary ends of the same condi- It is assumed that the flow of molecules leaving the
tions. Thus, the pore structure (l) exerts a considerable unit surface contains s-fraction of evaporating mol-
effect on the mechanism of vapour migration. The ecules and 1-a-fraction of reflected molecules. In the
value l is always positive, while s may be negative paper diffuse [-4] and specular reflections are con-
as well depending on the sign of the temperature sidered.
gradient AT along the capillary (s ~ 0). If s < 0, then
with 1 = - s the mechanism of vapour migration will (a) Diffuse reflection
differ from that at / = s. Hence, the direction of the With diffuse reflection, for a flow of molecules from
temperature gradient has an effect on evaporation the unit lateral surface of a capillary the following
Theoretical investigation of vapour transfer 963
equation is obtained [the flow is referred to the value The coefficients a 1 and a 2 are sought by substituting
j(1, To) = J 0 ] : (4) into (1) (assuming that % = ~) and equating the
coefficients at exp{lx} and exp{ - I x } :
Pe(T) ( T o ~ 1/2
I(x) = ~ Pe(To)\ ~ } exp{c} exp{-c} b exp{s}
al c-I a2 c+l $2-c 2 s - l '
The expressions for the functions K(x) and Kl(x ) are (Q/kTo)(AT/Tol) = + 1], the solution of equation (3)
given in [5] is expressed as follows
12X2+2 1 dK(x) b
K(x)=2(12x2+4)l/2 2 x' Kl(x)- dx I = a'1 exp{cx} + a 2 exp{ - cx} + ~ x exp{sx}, (4 l)
For nonisothermal capillary surface, if the surface where a t1 and a t2 as well as a 1 and a 2 in (4) are
temperature varies by the law determined from the system of algebraic equations
obtained after substitution of (41) into (1).
T(x) = To(1 + Ax) For the flow of molecules at the capillary exit find
Bexp - Q ~
Pe(X)= t kT(x) } where
C
"• j_ ..... -2-o7~
where s = - l
1111/~
i
o0.~
From (10a) it is seen that for l < l J ( 0 ) > 0 and
J(1) > 0, i.e. evaporation takes place at both ends of
/ a =0"8 the capillary and at l > 1 J(0) < 0, J(1) > 0, i.e. with
increasing x transition from condensation to evap-
c =0'[
oration occurs.
Expression (10b) indicates that for all I at x - - 0
evaporation occurs, for x = l evaporation takes place
at l < 1 and condensation, at l > 1.
2 4 6 8 lO
When evaporation proceeds only at the bottom with
{
diffuse reflection of molecules from the lateral sur-
FIG. h Flow N at the capillary exit vs I face, the flow I may be obtained from (1) assuming
with diffuse reflection (To = 21YK, l =
0~=0.
10-1 c m ) - - - A T = 0 c ; - AT = -10.
The calculations showed that for c~# 1 and AT = 0 (b) Elucidate the effect of specular reflection of molecules
the flow at the capillary exit at small I increases with l, on the net flow at the capillary exit
and then practically becomes independent of 1 (Fig. 1). The number of molecules that evaporated from the
In case of a # 1 AT # 0 the behaviour of the curves side surface and left the capillary after multiple specular
characterizing the flow dependence on / was more reflections, is written as follows [8]
complicated.
1
At the lateral surface the net dimensionless flow of
molecules is determined by
N w = 2~R21 i j(~,
do
T)SI(1 - x ) d x , (11)
--J(x) = I ( x ) - l ( x ) = ~ [ l - ( x ) - e x p { s x } ] . (7)
where
where I is a flow of molecules getting onto unit lateral
surface. I is sought from the equation
I-(x) =
fo' l ( ~ ) K l ( l x - ~ l ) d ~ + I o K ( x ).
1 exp{l(2x+fi-1)}- fl 1
-fl---1 /~, (9) S2(x)=Kz(x)+ (1-~)" K2 n ~ l -K2 '
n=l
where fl = s/l, and the positive value of J corresponds
to evaporation. Besides, the account should be taken of the molecules
It follows from (9) that the behaviour of J(x) is which left the capillary after they had evaporated from
determined by I and ft. Thus for 1 < fl < exp{/(fl- 1)} the lateral surface, got to the bottom and reflected
at x = 0 J < 0, at x = 1 J > 0. As to the case of specularly from it. They are allowed for approximately
Theoretical investigation of vapour transfer 965
through substitution by the diffusely reflected mol- from the other (X = L). The surface of liquid is char-
ecules acterized by the specular reflection coefficient a.
G L d2n
~ = n(x)-~I fo n(~)[exp{-l[x-~l} all[1-~+2~(exp{-(cl + l ) } - l) 1
No~ l 1 a
+ ~rexp{ - l(x + ¢)}] d~ - 2 ~ ° exp{ - Ix}
numerical calculations are presented for water with the This expression is a generalization of the known
following parameters: GL = 4 x 10-3; / = 0.1; o- = 0 Knudsen formula [15] for the case of evaporation
and 0'8; T = 300°K; p~ = 3430N/m2; p~ = 490N/m 2. from a finite length capillary. To compare, it should
As to the flows in case of G L being of the order of be noted that the exact Knudsen formula (L/R >> 1,
unity, the curve n(x) cannot be divided into three zones. o-= 0) includes coefficient 8/3, and when the expo-
The net flow of molecules at the capillary exit is nential kernel is used in (21), coellicient 2.
equal to the sum of surface diffusion flow N~{1)=
2~zRJ~(1) and flow of molecules N(1) emitting through (b) Nonisothermal case
the open end of the capillary. It should be kept in The values r and D~ are related with the surface
mind that at G R >> 1, N s >> N and at (;~ << 1 N~ << N temperature as follows [9]
(since G~ = 1/ER 2 characterizes the ratio of conduc-
tivities due to surface and Knudsen diffusion).
The expression for N is of the form r = z 0 exp u ) , D~=D~oexp
" - kT(x
N = 7rR2{NoK2(1)- N~[1 - a K 2 ( 2 ) ] ',
2rcR2no I fl Assume that T = 7o(1 +Ax) and A << 1. Then lin-
+ n(x)[K(1-x)+aK(l+x)]dx. (21)
T J0 earization and substitution of the variable
Here the first term describes a flow of molecules
that diffused from the bottom and covered the distance nx(X) = n(xjexp -
L without collisions. The second term is a flow of
molecules entering the capillary through the open end.
The third term stands for a flow of molecules which reduce.equation for n~ to the form similar to that in
reached the bottom without collisions, reflected specu- case of an isothermal capillary except for the fact that
larly from it and then emitted through the open end. in the left-hand side a term containing the first wtriable
The integral term characterizes the flow of molecules dn~/dx appears. Herein, the ratio of the coefficients
desorbed by the internal surface of the capillary and of the lirst and second derivatives
left it without collision against the wall and after
specular reflection from the bottom. AT ~: 2u
The comparison of the approximate analytical solu- 7'0 kT;~
tion of equation (14) and its numerical solution for
the exact function K(x) has shown that there is but Since from an approximate analysis [9] follows that
slight difference between the values of n(x) correspond- 1
<~,:/u ~ 23, and u/k T o >>1, the order of the magnitude
ing to exact and approximate expressions for K(x), of 7 is equal to A T / 7 ) ) x u / k T o. If ?,-~ 1, then at
this difference increasing with decrease of GL and GL(0) << 1, i.e. in case of short boundary layers the term
increase of/. As for the appropriated values of N, they containing the second deriwttive is much greater than
differ from one another in a greater degree than those the summand with the lirst derivative. Hence, the
of n(x) do. solution of the equation for ~h can be presented in
In (21), in order to decrease the calculation errors, the form
an exact solution for the function K(x) should be used
rather than an approximate one. For G~ << 1, however, ni(xlro
integration of the terms with a~ and a 2 yields a small "Ei
contribution into the value of N. To simplify in- i.e.
tegration, therefore, in (21) an approximate exponential
expression for K(x) may be particularly used (in the " )/ n~IxlrIx)
n(x) -~ nl(x)ex p h"l'(i~: zi (22)
summands including a 1 and a2).
With no surface diffusion, we have for N relation-
ship (21) wherein n(x) is the solution to integral everywhere but in the nearest vicinity of the open end
equation (17) at G~, = 0 with an exponential kernel, (where the temperature Tt effect appears due to the
i.e. it is a linear function. This allows easy calculation boundary condition at the exit (15)).
of the integral term in (21) with exact kernel K(x). The flow N at the capillary exit is expressed by the
In case of L > R and N~ = 0, particularly, obtained formula differing from [21) only by 1/r(x) includcd in
within R2/L 2 the subintcgral expression. Bccause of relationship {22),
7 R NO (1 nonisothermity has almost no ell'oct on the integral
N=~ L 1_o.+2 R \ 7 L] for IAI << 1. The tirst summand in (21) depends only
L on To. Two other ones containing the tlow N~ depend
968 A. V. LUIKOV, T. L. PERELMAN,V. V. LEVDANSKY,V. G. LE1TSINAand N. V. PAVLYUKEVICH
on 7'1-1/2 but since T1 = To(I+A ) and IAI<< 1 this and, with the above in view, is of the form
dependence is not significant. At low temperature
2Flctpe 1 ~L
drop the flow N, therefore, is independent of the non- N = [(2~m__m~t/z~_4fl_=n)[Lf0 n'(g)v
isothermity, while the surface densities n(x) for A = 0
and A :~ 0 are essentially different. Hence, in a non- p(]) L -
isothermal case the net molecular flow N + N~ differs -~ (2rcmkT)l/z. E 3 ( ~ ) l t E 3 ( x L - )
from the appropriate flow in an isothermal capillary
[since N~ = - [2~zD~(1)no/I] [dn/dx](1)}. + L [ ~'_n;(:)vE 2 ( L ( x _ ~ j ~ d g _ L [ 1 n'(~!v
The numerical solution to equation (14) for the case Jo 22 \2 / d:, 22
of ice evaporation showed the validity of the above
considerations and expression (22), in particular. As E2 ( ~ - x ) d?, (2rrmkT)l/2
to the cases of GL(0) ~ 1, i.e. the absence of boundary
layers, and of IA I ~ 1, i.e. high temperature drops, [L(1-x)~
X /2,3~ - - ~ , (23)
equation (14) was solved numerically to determine n(x)
and N. where
In a transient case, a flow of particles d e p e n d s on 5. W. L. Winterbottom, Vapor solid interactions and the
the c o o r d i n a t e a n d time. C o n s i d e r the case when effusion oven, J. Chem. Phys. 47, 3546 3556 (1967).
e l i = 1. U n d e r z e r o t h initial c o n d i t i o n s with the use of 6. A. 1. lvanovsky, Some interaction problems between
measuring cavity and a rarefied gas flow, Trudy Tzentr.
the L a p l a c e t r a n s f o r m a t i o n a n d the a s s u m p t i o n s m a d e Aerolog. Observe. 56, 49 96 (1964).
w h e n solving e q u a t i o n (23), it is easy to show that the 7. R. F. Strickland-Constable, Kinetics and Mechanism of
e q u a t i o n for a flow of molecules in dimensionless Crystallization. Academic Press, New York (1968).
c o o r d i n a t e s (t 1 = t/t*, t* is characteristic time of the 8. R. Berman and F. E. Simon et al., The thermal conduc-
tivity of diamond at low temperatures, Proc. R. Soc.
p r o b l e m ) is o f the form
220, 171 183 (1953).
4[2"~2c72N [2 ~2(p2N 9. J. H. de Boer, The Dynamic Character ~[ Adsorption.
Clarendon Press, Oxford (1953).
9 ~T) ~ x 2 -t-~c~* ) i~t~ 10. G. W. Sears, A note on the flow of gases through very
fine tubes, J. Chem. Phys. 22. 1252 1253 (1954).
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+N+2ct* Pt~- 3V-L ? ~ . (25) tribution to the total flow from a Knudsen cell, J. Chem.
Phys. 37, 784 793 (1962).
Since 2/L a n d 2/ct* are usually small, we retain in the 12. T. R. Bates and A. T. Forester, Coupled molecular flow
e q u a t i o n the t e r m s of the first o r d e r of smallness. Then and surface diffusion. Application to Cesium transport,
J. Appl. Phys. 38, 1956 1968 (1967).
e q u a t i o n (25) takes the form
13. A. S. Akhmatov, Molecular Physics of Boundary Friction.
2 ['N 1 2 ~n' Fizmatgiz, Moscow (1963).
N = -2 v 14. M. Van Dyke, Perturbation Methods in Fluid Mechanics.
ct* dt* 3 L ?x* Academic Press, New York (1964).
w h e r e the first term from the right a c c o u n t s for the 15. M. Devienne, Frottement et Echanges Thermiques dans
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diffusion with macrocapillary evaporation, lnzh.-Fiz.Zh. Phys. 46, 3199 3216 (1967).
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3. B. V. Deryagin, S. V. Nerpin and N. V. Churaev, To New York (1958).
the theory of liquid evaporation from capillaries, 20. R. Clausius, Kinetic theory of gases, in The Founders
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R~sum~ Dans la premi6re partie de I'article on 6tudic l'dvaporation capillaire dans des conditions de
r6gime mol6culaire fibre pour un cas non isotherme, en supposant que l'6vaporation se fait ~ la fois sur
la surface lat6rale et sur le fond. On consid6re deux modes de r6flexion sur la surface, soit diffus soit
sp6culaire. Dans les deux cas on obtient des expressions approch6es des flux de mol6cules fi la sortie du
milieu capillaire. Darts le cas de la r6flexion diffuse, on obtient h la lois le flux de mol6cules quittant
l'unit6 de surface et le flux net surfacique. On 6tudie la transition de phase a la paroi en fonction d'une
longueur adimensionnelle et dc la chute dcpression.
Dans la seconde partie, on montre que I'effet de la diffusion cn surface, sur la conductivit6 capillaire
est d6termin6 par lc param6tre adimensionnel (;L dgal an rapport de la racine carr6e de la moyenne
quadratique du d6placement d'une moldcule en surface, il la longueur capillaire. On traite l',Squation
int6gro-diff6rentielle initiale.
Dans la troisi6me partie bas6e sur la th6oric aFprochdc d[i libre parcours moyen, on trouvc une
expression pour un 6coulement de vapeur ,l travers un corps poreux fortement dispers6 quand le mod+le
capillaire n'est plus exact.
970 A . V . LUIKOV, T. L. PERELMAN, V. V. LEVDANSKY, V. G. LEITSINA a n d N. V. PAVLYUKEVICH
T H E O R E T 1 S C H E U N T E R S U C H U N G DER D A M P F U B E R T R A G U N G
D U R C H EINEN K A P I L L A R - P O R O S E N K O R P E R
Zusammenfassung lm ersten Teil der Arbeit wird eine Untersuchung der kapillaren Verdampfung unter
der Bedingung freier Molekularbewegung fiir einen nicht isothermen Fall behandelt, wobei vorausgesetzt
isL dab die Verdampfung an der Seitenwand und am Boden stattfindet. Zwei A r t e n d e r Reflexionen
yon der Obcrfl~ichc, diffus und spiegelnd, werden betrachtet. Ftir beide F~ille werden N~iherungsbezie-
hungen fiir den Molekularstrom am Kapillarende abgeleitet. Im Fall der diffusen Reflexion stimmen
dcr Molekularstrom an den Seitenfl~ichen und der rcine Oberfl~ichenstrom iiberein. Dieser Ausdruck
crlaubt Untersuchungen des Phaseniiberganges an der Wand, dcr yon der dimensionslosen L~inge und
dcr Temperaturdiffcrenz abh~ingt.
Im zweiten Tell wird gezeigt, dab die Wirkung der Oberfl~ichendiffusion auf die kapillare Leitf'~ihigkeit
durch den dimensionslosen Parameter GL bestimmt wird, der gleich dem Quadrat des Verh~iltnisses
yon mittlerer quadratischer Verschiebung eines Moleki~ls tiber die Oberff,iche zur Kapillarl~inge ist; dies
erg~,inzt die friihere Ableitung der integralen Differentialgleichung in ihrer Ausgangsform. Im dritten
Tell wird. wenn das Kapillarmodell zu ungenau ist, mit der N:dhcrungstheorie einer mittleren freien,
molekularen Wegl~inge eine Beziehung fiir einen Dampfstrom dutch einen hoch dispersen, por•sen
K 6rper angegeben.
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