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t5
C oncentrati ons ,
V el oc i ti es , and Ma
l)'
0t -
a* : diffusion vr
Thesediffusion velocitiesindicate
local motion of the fluid stream.
The notation for velocitiesin
16.l-2, togetherwith someuseful
It i s i mpor t ant t hat t he r eadert l
various kinds of velocities.There
representits behavior pictorially.
when liquid I evaporatesand diff
filled with vapor -8. As I evapo
there is not a clear dividing line b
as sugges t edin Fig. l6. l- la; ins
I
: h e M ech anis m s o f M a s s T r a n s p or t
t is appropriatethat in 916.1we
' concentrations,velocities, and
/olvesno new physical principles,
' r s t ud) o f th e l at er t opic s .
l, and the binary diffusivity 2on
ure and pressuredependenceof
.e diffusivities of binary gas and
cular point of view.
rostmixturesof interestmakes it
iluesof 9uu in most calculations.
neasuredvalues, since they are
2 p,,,
n
\s^
(16.1-1)
i=l
2r ru
(16.r-2)
T" .
i-l
Note that cu* is the local rate at which molespassthrough a unit crosssection
placedperpendicularto the velocity u*. we shall find extensiveuse for both
of theseaveragevelocities. Still other averagevelocitiesare sometimesused,
such as the rolume areroget'elocityur. (SeeProblem 16.K.)
In flow systemsone is frequently interestedin the velocity of a given
s p c c i esw i th respectto u or u* rather than w i th respect to st at ionar y
coordinates. This leadsto the definition of the "diffusion velocities":
at - o:
O N S , V EL OCIT I E S ,
4gl
ui -
o* :
( 16. 1- 3)
(16.1-4)
TABLE I 6./ - I
P : pA + p./r :
PA :
r.\
(B)
o.
:U
@1
: mass fraction of I
It
3a
3t
(C)
a\
ll
P
a
(D)
J!-a-!
,l l l l
E
,"
Pi
io:
mo lef r ac t ionof I
'o:;:
At -
p
'
(E)
*i
!<i
5'n\
(F)
r0t
:u
(G)
tn
o
r_ 4+rB:I
( H)
rr1 M1
xB MR:
( ua
(r)
z
a
(1)
oalaS:l
an
:------+-:1
M;
Mrt
M
i4
(,()
ra : ---A !
-:+j
M,
M,
r,M,
(L)
(,th
@A:
rnMn
* r3M j
o.
z:
()3
ad
rl
5
!4
.. x
U7
M^
Ja
co
(M)
'!
a
. ^'t
-,
. -l
-a
l rl l
::J
't
a'\-
td.
J
M,B
da,
u*l
*^*"(ft.
( N)
do,^:#:#r"
E
o
z
(o)
\
Oa
9O
ex
3
<
o-
>.
qd
a-
TABLE I 6. I - 2
NOTATION FOR VELOCITIES
IN BINARYSYSTEMS
(A)
\
(B)
(C)
(D
(C)
.9
o^q
^alaE
qi
\d
.96
i,
o;
Y=
v:
o P x1 I,i
I
E
E
I
I
I
t
498
oooa
'6
9, : . P+
ts -
<V
JE'z'
av
lttl
=a
fi
[:
(
ri
?Id
9tovdi
yo2ho=oo
F: P
;>
sqorlrug ?p JrsPfl
---
i-l
v a{.J
) NS IN B I NA RY S Y S T E M S
rn (g/cm3)
.^_Qs
\U
'
>l>
(A)
(g of Alcms of solution)
(B)
o
o
o
qa
(c)
*1
(D)
(E)
ll
*i
ll
+*
il
.-i
5'5\
i l tl
l<
v.e
ts,E
^F \
:U
Ft
ua
__
@t:
,tMt
* rrtMn
*a
ll
iz
!1?
(K)
,:\
z
a
Ur
.r ,M,
(1)
(up
+_ _ _ a
Mt 'M B - M
j
'\
-l-
a
q
a1 * a o : l
'\
< t<
(c)
frt of mixture
\a
Els l'.
:,++
*i
''1
' \<
z
i
-'
Xo
l tl l
.*
ll
.V
a-
Itrl
l
I
g-molesof Af cm3 of solution)
al
3-
ion (g-moles/cm3)
r q- - -
sv
1t q
'q
-f
,-,
T1
q
.l
.{\
++
":
llll
(M)
-!'l
oe
l l rl
tl
II
.i
-'l
P-J
al:
-{
' {-ll > > t<
llll
'!i
. -l
o
:
o
z
M, M -dr,
.
" -A - k AMA + xB lt4u y
d, , ,
\
A
T\
!r<
O6
-X
8<
^a
o. >c,l <d
llll
s '3
2
N BINARYSYSTEMS
:o stationarycoordinaies
relativeto u
relativeto o*
jz
l ttl
76
!f
e'z
itr'Z'
(A)
(B)
-^
(c)
.9
\i
'-ooaw) 9 , l 6
^ a a C^ q
Gi
o'P xr
.98
R+
Y:
ir
;.;
":
5-q
.:d
F: P
Ytr 4- c dT
y ( J 2baEd,o
(n
(c)
t
i
'-
6AY
IJ ^.F + r5
qa6A
r8 6 5
E.i P r
iq
( !GL G
d^
o50E
tr aotr uo
5-5A(n
Es
o tr
'oEt"
<
E
o
cE
cP
'- :'- ;- cd
Er
6 6 o "a l
q
X
J
-LLI!IJ.II.
X >,
=<. -
c E
o' X
J.r'
El
o
3+
4ln
X.-I
=-
=I
and the Mechanisms
Diffusivity
500
of Mass Transport
dii
o
ll
I
a
I
s
.\'
tl
C oncentrati ons ,
V el oc i ti es , and Mas
ir* : pr(a
Jn* : cr(u
Velocityvectors
Jr* : ct(a
Fig, l6.l-1.
I ncorrect
Correct
(a)
(b)
: ci u t
Ptot
mass
(16.1-5)
Nn:
cPi
molar
(16.1-6)
p n (u n - a )
J t:c t(a i -u )
mass
(16.1-:1)
molar
(16.1-8)
,i
r e Mech anis m s o f M a s s T r a n s p o rt
Co ncentrati ons,
S OI
and the mass and molar fluxes relatiue to the molar-auerapeuelocitv u* are
jo* - pr(uo- a*)
mass
(16.1-e)
Jo* :
cr(uo- u*)
molar
(16.1-10)
The notation for fluxes in binary systemsis summarizedin Table l6.l-3,
together with some relations among the various fluxes. It should be
emphasizedthat the definition of a massflux is not completeuntil both unirs
and referenceframe have been given.
Mathematically speaking, any one of the foregoing six flux notations is
adequatefor all diffusion problems,but each has certain advantagesand all
have appearedin the literature. The flux N, (and to a resserextent n,)
h a s been used i n engi neeri ngbecausei n processcai cul ati onsit is usually
desirableto refer to a coordinatesystemfixed in the equipment. The fluxes
frand' Jr* are the usual measuresof diffusion ratesand aie usefulin formulating the equations of change for multicomponent systems. The fluxes
J, andj r* are seldomusedbut are includedherefor the sakeof completeness.
We use N, in most subsequentdiscussions.
Example l6.l-1. Relations Among
the Molar
Fluxes
ct(ur-
u*)
(b)
e cif icti me in a dif f u s i n gs y s t e m .
Application
-^,
( 16. 1- l)
l
then gives
,L
Ji *:N ;-"i IN i
(r6.1-12)
j'
From this result it can be seenthat the molar diffusion flux Jo* is simply the difference between the molar flux N, and the rate of bodily transport rtult flow) of
speciesi due to the local molar flux of the mixture. Equation 16.1-10 mav be
similarly interpreted.
b. Summation of Eq. 16.l-12 from i : I to i : /, grves
1l
rss
(16.1-5)
I"r,*: o
rlar
(16.1-6)
,ss-auerage
uelocity u are
mass
(16.r-7)
molar
(16.1-8)
Jo* : -1n*
An application of this result is given in Problem 16.I.
(r6.1-1
3)
( 16. 1- 14)
502
0 1 6. 2 F lc K ' S LA W OF D IF F U SION
In E q. l. l- 2 t he v i s c o s i typ i s d e fi n e da s th e p roporti onal i tyfactorbctrvcen
mo m ent um f lux an d v e l o c i tyg ra d i e n t(N e w to n ' s l aw of vi scosi ty). In E q.
8 .1 - 6 t he r her m al c o n d u c ti v i tyk i s d e fi n c d a s the proporti onal i tyfactor
g ra d i en t (F o u ri e r' sl aw of heatconducti on).
b e tweenheatf lux an d te m p e ra tu re
T ABL E I6 .2 _ I
E Q U I V A L E N T F ORM S OF F ICK' S F IRST L AW OF B IN A R Y D IFFU S ION
Flux
Y at,t
nA
N/
Y",t
it
Ya tn
J,t*
Y' t
j t
vr_l
J,t*
c\un -
G r a d ie n t
ll3)
n ., N,, ia
J,,t* :
i::
o t,( n .,
n73) :
r _ ,( N., + N 1)
- p !/
-p!1 4rrV ot .,
:
-c?,r,,Y :.,
(A )
(D)
- c? ,tttVa :^
(B)
' (c )
a sVo ,,
i, , u:
- 9. , o*
dq
O,rl
,l
r,,,:
-v
u
-
(pt' r)
aa
lc2\
-\;)r'r,''.r/,V'.r
(E)
4u :
/p2\
Vr,tn
J .rr:
Vr',1
c (u, { -
ut t l :
1 'V t ;
(F)
(G)
-{t ,li
- 0";
( PC, T)
4A
D IFFU
EXPER IM EN TAL
Gas Pair
co2-N2o
co2-co
co2-Nr
Ar-O,
H2-SF6
Hr-CH1
t h e pr o p o rti o n al
it y f ac t orbet w c e n
le w t on' sl a w o l v is c os it y ) . I n Eq .
n e d as th e p ro por t ionalit yf ac to r
( F ourier'sl a w o f heatc onduc ti o n ).
- LAW O F BI NA R Y D I F F U S I O N
Fo rm of Fic k ' s F i r s t L a w
, ( .nt *
n 1) :
-p !
, ( N , r + N 1) :
-1yVtu 1
-c!1 ,, 1,Y.r,,
(.4)
- c9 nrrV t : . ,
( D)
i .r,:
-f| ,tn4
'rar:
d
-v ; (pr,)
aa
t .2\
,,t ,, ,, V .r .,
lt[^M
l 12
l:^
-,
l L ,,,,Y ' u. ,
\,4t v r, | t v r I
(E)
c'J , ,,
( F)
(G)
: 9, . r i n a b inar y s y s t c ntin a n
( 16. 2 l )
,V r -,
n i n t erms o f th c m olar dif f Lrs i o n
; I d if f u se s(mov esr elat iv et o th c
le lr ac t i o no l ,1 ,jus t as heatf lo w s
1 gt emPe ra tu rc .
riv a lentsta te m ent sof F ic k ' s fi rs t
s om cof th e m a r e s r r m m ar iz e di n
iffusivity.(r,,,, is ilentical in all
the f ollo wi n gch apt c r sis t hc f o rm
rlar f lux re l a ti vct o s t at ionar yco - c 9. r, ,Vr,,
O.rl
dy ' "
4 u : -u rt f c C" rl
ll
u) :
503
which is the molar flux of I resulting from the bulk motion of the fluid,
and the vector Jr* : -c9,ttYr,,
which is the molar flux of I resulting
fr om the di ffusi onsuperi mposed
on the bul k fl ow . Thus i n Fig. 16. 1- 1bt he
bulk flow and diffusion terms in Eq. 16.2-2 are in the same direction for
species,4 (because,4 is diffusing with the current) and are opposed for
species,B (becauseB is diffusingagainstthc current).
The units of the massdiffusivity9,r, arecm2sec I or ft2hr 1. Note that
the ki nemati cvi scosi tyl and the thermaldi ffusi vi tya al sohavethe sam eunit s.
The way in which thesethree quantitiesare analogouscan be seenfrom the
following equations for the fluxes of mass, momentum, and energy in
systems
:
o ne-di mensi onal
(B)
' (c)
? , , , Yu,.
( 16. 2 -2 )
( 16. 2- 3)
(16.24)
(F o u rie r'laswf o r c o n s t an
t ) O e. z - s )
pe
Theseequationsstate,respectively,
that (a) masstransport occursbecauseof
a gradientin massconcentration,(6) momentum transport occursbecauseof
a gradient in momentum concentration,and (c) cnergy transport occurs
bccauseof a gradi enti n energyconcentrati on.Theseanal ogiesdo not apply
in two- and three-dimensionalproblems, however, becauser is a tensor
quantity with nine components,whercasj , and q are vectors with three
components.
In Tables 16.2-2,3, and 4 some valuesof f)u, are given for a few gas,
TABLE I6.2-2
E X P E R I M E N T ADLI F F U S I V I T I E
OSF S O M ED I L U T EG A S PAIR Sa
g
Temperature
tn
('
(cm2
K)
Gas Pair
sec-r)
co2-N2o
co2-co
co2-Nr
Ar-O,
H2-SF6
H2-CH1
273.2
273.2
273.2
288.2
298.2
293.2
298.2
298.2
0.096
0 . 139
0 . 144
0 . 158
0 . 165
0.20
0.420
0.726
Temperature
TAELE t6.2-3
DI
EXPERIMENTAL
B
Chlorobenzene
Bromobenzene
r('c)
10.01
39.97
Ethanol
Water
Water
n-Butanol
9ou x lO5
(cmzsec-r)
25
30
0.0332
0.2u2
o.st22
0.t617
0.9652
1.007
1.069
1.146
1.226
1.291
0.0332
0.2@2
0.5122
0.7617
0.9652
1.584
1.691
1.806
1.902
1.996
0.05
0.275
0.50
0.70
0.95
I .13
0.41
0.90
1.40
2.20
0.13I
0.222
0.358
0.454
0.524
| .24
0.920
0.560
0.437
0.267
System
He in SiO,
He in pyrex
H, in SiO2
H, in Ni
Bi in Pb
Hg in Pb
Sb in Ag
A1 in Cu
Cd in Cu
POet
(p"np"u)%(T"eT,tf/'
cm2sec-l,p I
in which 9uol:f
mental data gave the following'
For nonpolar gas-pairs:
;
For HrO with a nonpolargas:
h e Me ch anis m s o f M a s s T r a n s p o r t
Temperature
and Pressure
Dependence
of Mass Diffusivity
TABLE I6.2-4
-3
{' THE LIQUID STATEA
IN THESOLIDSTATE"
DIFFUSIVITIES
EXPERIMENTAL
gnu
ilA
x IOE
(cm2 sec-r)
0.0332
0.2642
0.s122
0.7617
0.9652
1.007
1.069
t . 146
1.226
1.291
0.0332
0.2&2
0.5122
0.7617
0.9652
1. 584
1. 691
1. 806
1.902
1. 996
0.05
0.27s
0.50
0.70
0.95
0 .1 3 1
o.222
0 .3 5 8
0.454
0.524
1. r 3
0.4r
0.90
1. 40
2.20
1. 24
0.920
0.560
0.437
0.267
Diffusivity,9nu
(cm2sec-l)
r('c)
System
He in SiO,
He in pyrex
20
20
500
2 . 4 - 5 . 5 x 10 - 1 0
4 . 5 x l 0 11
2 x 10-8
H, in SiO,
H, in Ni
500
85
165
x1 0 8
0.6-2.1
1.16 x 10 8
10.5 x l0-8
20
20
20
20
20
Bi in Pb
Hg in Pb
Sb in Ag
Al in Cu
Cd in Cu
l.l
2.5
3.5
1.3
2.7
x
x
x
x
x
l 0 rG
l 0 15
10-21
10-30
10-15
PQar:
(r n)%,
(p,np o)%
"
".q.r
" (h.
" ( J-I-T_T;)'
(r6.3-r)
i,)"
in which 9,to[:] cm2 sec-l, I [:] atm, and 7 [:] " K. Analysis of experimental data gave the following values of the constants a and b:
F or nonpolar gas-pairs:
a :2.745 x 10-4
b : 1.823
For HrO with a nonpolar gas:
a:3.640 x 10-a
b :2.334
1J. C. SlatteryandR. B. Bird,A.I.Ch.E.Journal,4,137-142
(1958).
506
Diffu sivity
E x a m p l e 1 6 .3 - 1 . Esti m a ti o r
I (argon)
B (oxygen)
(p"eprn)'A: (4
Therefore
1.0
- 7 " =, r.0-
(T"AT,i%' : (l:
b--
0.9
G--
0.8
| \tA
\r ^ . *)
0.7
pD
06
tr\b
a\:l
\l
: 2.
T"A TrR l
: 9.
fpof o.s
Substitutionof thesenumericalva
0.4
0.3
0.2
0. 0) aaB: ( 9. 0
9 ta : o'18
The measuredvalue (Table16.2-2
1.o
0 .1
0
0I
: (/ ,
methodbasedon kinetictheory.
0.15 0.2
i.5
2.0
3.0 4.0
p/pc
E x a m p l e 1 6 .3 - 2 . Esti m a ti o t
"
I, : 190
T, : 305'
methane:
ethane:
uri P c t:'
,_|
n
r,-S -r
t;
i :t
*; t
ri
....l.-F
the Mechanisms
of Mass Transport
507
E x a m p l e 1 6 . 3 - 1 . E s t i m a t i o n o f M a s s D i f f u s i v i t y a t L o w D e n si ty
Estimate g oo for the system argon-oxygen at 293.2' K and I atm total pressure.
Solution. The propertiesneededfor Eq. 16.3-l (seeTable B-l) are
MTCPC
I (argon)
B (oxygen)
Therefore
ln_
151.2
154.4
39.94
32.00
48.0
49.7
13.36
h-
=D--
I \' ,
lt
l \rr
/ 1
:l _* _l :0.2372
l _+ _l
' 32.00/
M nl
\M,t
\39.e4
293.2
/
T
\,
/
\r.82 3
x l 0 {l :l
al -:l :2.745
x154'
4/
\!T" tT,n/
\V l 5l .2
: 9.01 x lO-a
1.4
=q
t.2
Substitution
of thesenumericalvaluesinto Eq. 16.3-l gives
t.n
methodbasedon kinetictheorv.
r 0.8 1.0
1. 5
3.0 4.0
tp
^c
o f M a s s D i f f u s i v i t y a t H i g h D e n si ty
Estimate g n" for a mixture of 80 mole per cent methane and 20 mole per cent
ethane at 200o psia and 104" F (136 atm and 313" K). The experimentalvalue of
(pQ ap)o at 293' K is 0.163 atm cm2 sec-r.
Sof ution. First correct the given value of (p97)o to the desired temperature,
using Eq. 16.3-1 with the nonpolar constants:
/313\ 1.823
T" : 190.7"K,
r, : 305.4'K,
methane:
ethane:
p, : 45.8atm
p" : 48.2atm
p; :> ni pc;:
t:I
: 46.3atm
n
a'
ztts:
r'47
e,tn:
o f Ordi nary
D i frus i on i n t
The pseudo-reduced
pressureand temperatureare
p
136
' :_ :2 .e 4
46.3
P"'
T
313
Theory
= 0.7:.
(0 . 7 3 )
fpr*1o: 136
:9.9 x 10-4cmzsec-l
An observedvalue of 9tn:8.4
x 10-a cm2sec-lhas been reportedat these
conditions.sIf (pOn)o is predictedby the Chapman-Enskogtheory
givenin $16.4,
9ru is predictedto be 8.8 x l0-a cm2sec 1,which is unexpectedly
good agreement.
$ t6. 4 T HE O Ry O F OR D T N AR YD tF F U S| ONt N GA S E S
A T LO W D E N S IT Y
The mass diffusivity I .ru for binary mixtures of nonpolar gasesis predictable within about 5 per cent by kinetic theory. Again, as in $$1.4and
8.3,we begin with a simplifiedderivationto illustratethe mechanismsinvolved
arld then present the more accurate results of the Chapman-Enskog theory.
Considera large body of gas containingtwo molecularspeciesA and A*,
both specieshaving the same mass ,??_.1
and the same size and shape. Such a
is
pair
closely approximated by two heavy moleculescontaining different
isotopes, such as U235Faand U238Fu. We wish to determine the mass
diffusivity9r,o. in terms of the molecularpropertieson the assumptionthat
the moleculesare rigid spheresof diameterr{r.
As before, we shall use the following resultsof kinetic theory for a purer
rigid-spheregasat low densityin which thc temperature,pressure,and velocity
gradientsare small:
il :
7 :
/8" '"-'"
J'
Tm
f,nu
.l
--=^ - \J
l^
ljr
mc a n m o l e c u l arspeed
re l a ti v eto u o r u*
(16.4-1)
(16.4-2)
(16.+3)
Fi g. l 6.,Ll .
Mol ec ul artrans P o
Ntu : l.pr.r,
r,
A- n
frtl , - ,
,olo*,
he Mechanismsof MassTransport
are
T heory
of Ordi nary
509
.94
o:34
1 .47
i we obtainpgaal(po,")o .. 0.73.
0 . 184
:136 (0 .7 3 )
(16.4-4)
^-l
at these
rman-Enskog
theorygivenin 916.4,
ch is unexpectedly
good agreemenr.
O N I N GASES
<tures:-f nonpolar gasesis pretheory. Again, as in $$1.4and
lustratethemechanisms
involved
cf the Chapman-Enskogtheory.
wo molecularspeciesA and A*,
he samesizeand shape. Such a
' moleculescontaining different
e wish to determine the mass
'opertleson the assumptionthat
that are of sp ec i es
A ts x^l
^ll-a
(16.4-r)
sion frequency
lrea in
F gAS
(16.4-2)
e path
(16.4-3)
Eqs. 16.4 1,2,3, and 4 remai n val i d i n thi s nonequi ri bri umsit uat ion.
The
molar flux, Nr, of speciesl. acrossany plane of constant y is found
by
counting the moleculesof I that cross unit area of the plane in the positive
y-directionand subtractingthe number that crossin the negativer/-direction.
Thus
N ,l u : l o{rr,,r,* l u + f,,rc nal ,-, -
( 16. 4- 5)
)ompressed
Binary GaseousSystems,
o) to praneat y .
2^fu,
ray
:
x.r lr +n
' .r 1,*:,
(16.+6)
(16.4-7)
510
N ,r * N ,* (see
lrO^k
(16.+8)
(16.4-e)
+ilA
Evaluation of a and l, from Eqs. 16.4-l and 3 and use of the ideal-gaslaw
n : cRT : llrl sives
(16.4-10)
which represcntsthe mass diffusivity of a mixture of two speciesof rigid
spheresof identical mass and diameter. The calculation of 9;r' for rigid
spheresof unequal mass and diameter is considerablymore difficult; the
correspondingresult2is
?,,,::(q)'(+
* +)'' , T"',,
,,,
r \ 7r'
\ z nt 1
t nt R'
(16.4-11)
p\ u ' t r o n ) -
c 9,tt:
2 .2 6 4 6x 1 0 -s
^lwil
(16.4-12)
o ,a p 2 { )e,-aB
Theory
o f Ordi nary
D i ffus i on i n (
9m : 0'0018
in which 9uof:l
cm2sec r, c
o,tnl.:lAngstrdm units, and (
temperature and of the intermo
I and one of B. lt is convenie
Lennard-Jonesfunction:
v'qn(r): 4
e,lB t
5By nonreacting
we meanheretha
-.-z
Theory
1 -^ d r,
,
' "3
, ,)du
--cu y'" "
)''4
P Ct,t-
06.4_s)
(r6.4-10)
(16.4-rr)
he massdiffusivityvariesinversely
vith experimentaldata up to about
6.3-1.) The predictedtemperature
riscosityand thermal conductivity,
ve only; for accurateresults, the
be used. The Chapman-Enskog
t iv i ty we reg i ve n in ggl. 4 and 8 .3 ;
the gaseousstate at low density
RilA
oa62 {)s,,1p
9ta :0.0018583
Diffusion
(16.,t-8)
nA
of Ordinary
(16.4-r2)
"'( M"
.h)
P6.qnzQs,a.n
(16.4-r3)
i n w hi ch- ?uol :l
cm2sec-l , c [:] g-mol escm-3, ?n[:] ' K , p [ : ] at m ,
oanl:lAngstrcim units, and Qr.no is a dimensionlessfunction of the
temperature and of the intermolecular potential field for one molecule of
A and one of ,8. It is convenient to approximate this potential field by the
Lennard-Jonesfunction :
o,^,1(T)"v,,n?):
(TI]
(16.4-r4)
Table B-2 gives Q",.r' for this potential energy model as a function of
rc.Tfeuo. From these results one can compute thatQuu increasesroughly as
the 2.0 power of T at low temperaturesand as the 1.65power of I at very
high temperatures.(CompareEq. 16.3-1.)For rigid spheres,Qr.uuwould be
unity at all temperaturesand a result analogousto Eq. 16.4_ll would be
obtained.
The Lennard-Jones parameters ouo and ero could, in principle, be
determined directly from accurate measurementsof guu over a wide range
of temperature; with somewhatgreaterdifficulty,other measuredproperties
of mixtures of A and.B could be used. Suitable data are, hovrever,extremely
rare; therefore, one usually has to estimate o"o and euu. It turns out that
fairly satisfactoryestimatescan be made for nonpolar, nonreactingbmolecule
pairs by combining the Lennard-Jonesparameters of speciesA and B
e m pi ri cal l v:6
6Ar]:
'uo
$(o, * orr)
: J
'n, n
(16.4-1s)
(16.4-16)
=..|-F
D i ffusi on i n Li qui ds
513
This gives r.Tlea} :293.21118.5:2.47, and from Table B-2 we then obtain
ae,as : 1.003. Substitutionof the foregoingvaluesinto Eq. 16.4-13gives
t-----:-
r'!fU".
oe'Qs,'c
06.4-17)
(16.,t-18)
6 Qu
r of Mass Diffusivity
sity
gon (l) and oxygen(B) at 293.2'K
iollowingconstants:
^
A;
-3 :
1 2 4' K
:0.0018583@
"/tzrl.zx1-
l\
+, lz^oo/
: 0.188cm2sec-l
This comparesfavorablywith the measuredvalueof 0.20cm2sec-rgivenin Table
16.2-2.
S OR D TN A R YD | FFU S | ONtN L| QU TDS
$t6.5 TH E OR TE OF
In the absenceof rigorous theory for diffusion in liquids, there are two
rough theories that have been useful in making order of nragnitudeof calculations: the hydrodynamicaltheory and the Eyring theory. (We have already
given some results of the theories of Eyring and co-workers in connection
with the calculation of viscosity and thermal conductivity of liquids.)
The hydrodynamicaltheory takes as its startjng point the Nernst-Einstein
equation,l which states that the diffusivity of a single particle or solute
molecule of I through a stationary medium ,B is
9,sn:
"rfr
(16.s-1)
in which u,afF,1 is the "mobility" of the particle of I (that is, the steadystate velocity attained by the particle under the action of a unit force). A
relation between force and velocity for a rigid sphere moving in "creeping
flow" (that is, Re ( l) may be obtained from hydrodynamics. If the
possibility of "slip" at the sphere-fluidinterface is taken into account, thenz
F,t:6tltnu^^^\ffffi)
(16.s-2)
A; ? : tt:'r
K
5l {
6n\sutRt
(16.5-3)
9z.n\n
(16.5-4)
6nR,1
rT
4t[tnutR,t
(16.s-5)
xT
(16.5-6)
4nRa
If the moleculesare all alike (that is, self-difusion) and if they can be assumed
to be arrangedin a cubic lattice with all moleculesjust touching,then2Ro
may be set equal to (lolfr)% and
z-EsLt,t:
lfII'
xI
(16.5-7)
2n\Vu/
It has been shown5 that Eq. 16.5-7 predicts the self-diffusiondata for a
number of liquids within about f 12 per cent; that comparison includes
liquid metals,and molten sulfur.
associatedsubstances,
polar substances,
It is thus seenthat the simple hydrodynamicalapproachgivesexpressions
for the diffusion coefficient for spherical molecules in dilute solution and
also for the coefficientof self-diffusion. The theory further predicts that there
should be a variation of 9uB with the size of the diffusing species' The
hydrodynamic theory suggeststhat the shapeof the diffusing speciesmay well
be important, since the friction factor increasesby a factor of about 2 as the
length-to-width ratio of a body goes from I to 10'
The El,ring rate theoryt attempts to explain the transport phenomena on
the basisof a simple model for the liquid state. It is assumedin this theory
that there is some unimolecularrate processin terms of which the diffusion
{ W. Sutherland,
(1905).
Phil.Mag.,9'781-785
5J. C. M. Li andP. Chang,
(1955).
518-520
Phys.,23'
"/.Chem.
6S. Glasstone,
McGraw-Hill,
K. J. Laidler,and H. Eyring,Theoryof RateProcesses,
IX.
Chapter
NewYork(1941),
D i ffus i on i n Li qui ds
Est im at io
E xam ple 16. 5- 1.
for a Binary Liqu
Estimateg no for a dilute solutionof TN
l 5' c.
515
).A
(16.5-3)
(16.s-4)
A
(l
(16.5-5)
(16.5-6)
)-
(16.5-7)
D i ffusi on i n Li qui ds
+:(il)"
(16.5-8)
( 16.5-e)
This relation differs by a factor of 2zr from Eq. 16.5-7, the expressionfor
the self-diffusioncoefficientaccordingto the hydrodynamictheory; but Eq.
16.5-7 has been shown to fit the experimentaldata better than Eq. I6.5-8.
RecentlyLi and Chang?have suggesteda modificationof the Eyring theory
in order to account for the discrepancy.
Becauseof the approximatenature of the foregoingtheories,a number of
empiricalrelationshavebeenproposed,sone of which we mention briefly.
Wilkee has developeda correlation for diffusion coefficientson the basis
of the Stokes-Einsteinequation. His results may be summarizedby the
following approximateanalyticalrelation,l0which gives the diffusion coefficient in cm2sec l for small concentrationsof I in B:
Here Va is the molar volume of the soluteI in cm3 g-mole"r as liquid at its
rp, is an
normal boiling point, pris the viscosityof the solutionin centipoises,
"associationparameter"for the solventB, and Zis the absolutetemperature
o
in K. Recbmmendedvaluesof tyo are 2.6 for water, 1.9 for methanol, 1.5
for ethanol, and 1.0 for benzene,ether, heptane,and other unassociated
solvents. This equation is good only for dilute solutionsof nondissociating
solutes; for such solutionsit is usually good within -f 10 per cent.
If the readerhas by now concludedthat little is known about the prediction
of densegas and liquid diffusivities,he is correct. There is an urgent need
both for their own value and for developfor experimentalmeasurements,
ment of future theories.
E sti mati onof MassD i ffusi vi ty
E xampl e 16.5-1.
for a B i nary Li qui d Mi xture
in benzeneal
Estimategoufor a dilute solutionof TNT (2,4,6-trinitrotoluene)
1 5 ' C.
? Li and Chang, loc. cit.
8 See, for example, R. C. Reid and T. K. Sherwood, The Properties of Gasesand Liquids,
McGraw-Hill, New York (1958), pp. 28+298.
(1949).
'0C. R. Wilke, Chem. Eng. Prog., 45,218-224
10C. R. Wilke and P. Chang, A.l.Ch.E. Journal, l,26+270, 1955.
--Z
Pr o bl ems
P R OB LE MS
1 6 .A1 P redi cti on of Mass D i ffusi vi ty for a Gas-P ai r at Low D ensi ty
Predict 9n" for the methane-ethane system at 104" F and I atm, using the ChapmanEnskog theory. Compare your result with the experimental value given in Example 16.3-2.
A nsw er: 0. 166 c m! s ec -I
l6 .Br
78.11)'/,(213
+ 15)
0.705(140)0.t,
iec-1
e d val u e of 1. 39 x 1 0 5 c m 2 s e c - l .
5 t7
DI SC US S T O N
e diffusion to occur?
o n?
1 . l6 .l -l
at Low D ensi ty
A v al ue of 9uo:0.151
cm, sec'1 has been reportedr for the system C Or-a i r at 293. K
a n d I atm. E xtrapol ate gnoto 1500" K by the fol l ow i ng methods:
a. Eq. 16.3 1.
b. Eq. 16.4-11.
c. Eg. 16.4-13.
wit h t he a v e r a g ev e l o c i t y d e fin e d
properti es
Predict 9 uo for the situation of Problem l6.,4, by the following two methods :
at H i gh D ensi ty
2-3?
the statementconcerningthe temperature
predictingthe intermolecularforce field
?
lby the Stokes-Einstein
equation? Verify
rd p for gaseswith that for liquids.
d value of 9"" from Eq. 16.4-13would
er"fx1
rat the mole fraction gradient Vo, is noF
Explain.
f Schroeder
as quoted by R. C. Reid arfd
ids,McGraw-Hill,New York (1958),p. $1.
16.5-9.
T h e densi ty of aceti c aci d at i ts normal boi l i ng poi nt i s 0.937 g cm- 3. (A n ex peri mental
value of 0.91 * 0.04 x l0 5 cmz sec-r has been reported.r)
I5 .F r
5! 5
P robl ems
Solution. Use the equation of Wilke and Chang, taking TNT as comPonent
I and benzeneas component B. The required data are
p : 0.705 cp (for solution considered as pure benzene)
l,t : t40 cc g-mole- I for TNTll
T n : l'O for benzene
MR :78' 11 f or bc nz c nc
Sub stitu tionin E q. 16. 5- 9giv es
1 .3 8 x 1 0 5 cm 2 se c I
PR
16.A r
F OR DISCUS S ION
C orre c ti on
of Mas s D i ffus i v i ty
I6,D r
Predict 9
l 6.E r
C orre c ti on
of Mas s D i ffus i v i ty I
47, 1253(19s5).
2 Inlernational