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r8
for a B i nr
O F CO N
$r8.t TH E EQ UATTO NS
A BI NARY M I XTURE
ti me rate of c hange
of mass of A in
volume element
a^
-"i4 A
ot
input of .4 across
face at r
fiatl,
outirut of ,4 across
faceatrl L,z
nt , lr -
rate of production
of A by chemical
reaction
ra L,t
opo (4,
ra - --\a r -i
?* o
ot
CHA P T ER
r8
l or a B i nary Mi xture
tnge
Systems
n ordinarydiffusionwere formulated
diffusingspecies.In this chapterwe
n arbitrary differential fluid element
I f or t h e two c hem ic als pec ie si n a
for the massflux
r of the expressions
of forms. Thesediffusion equations
ms in Chapter 17 and more complins of ordinary diffusion for a binary
'the equationsof changefor a multi.ionsand heat effects,which include
rical speciespresent,the equation of
lance. These relations supply a full
:e m sand i n cl u det he equat ion sg i v e n
They are not normally used in their
usesthem by discardingterms that
ible and by this procedureobtaining
on underconsideration.
I equations,we are then in a position
Y!:! Lx Lu Lz
^,
ot
(18.1-1)
input of ,4 across
face at r
n1,1,L,YL,z
(18.1-2)
output of ,4 across
fa c e atrl L,r
nnrl r* 6, LY Lz
(18.1-3)
rate of production
of A by chemical
reaction
ro Lr Ly L,z
(18.1-4)
There are also input and output terms in the gr-and z-directions. When the
entire massbalanceis written down and divided through by Ar Ay Az, one
obtains. after lettine the size of the volume element decreaseto zero,
: ,,
**ou *':""\
*ol * (L?.
\or
oz/
( 18.1-5)
oPn
+ (V' ne) : ra
0t
(18.1-6)
55 6
S ystems
" YB + (V' n -) :
0t
r-
(18.1-7)
3
*(v'Pu):o
OT
( 18.1-8)
which is the equationof continuityfor the ntirture. It is the same as that for
a pur e f luid giv en i n E q .3 .1 -4 . In o b ta i n i n gE q . 18.1-8,w e have made use
o f t he r elat ion n1 * n n : p u (Eq . J i n T a b l e 16.1-3)and al so the l aw of
conservationof mass in the form 11 | ro: Q. Finally, we note that Eq.
1 8 . 1- 8bec om es
(18 . 1 -e )
(V'u):0
dI
+ p.N7):
R,,
(18.1-10)
for a B i r
*OT * ( v ' p - , u )=
e"
? + tv'c-,ur; =
dt
(1 8 . r-1 1 )
gives
Additionof thesetwo equations
(Rr R')
fi* f,'ca*): +
0r'
(18.1-12)
for the quationof continuity for the mixture. Here we haveusedthe relation
N/ + Na : ct)*. However, since moles are not in general conserved,we
cannot set R,a f R, equal to zero unlessone mole of ,Bis produced for every
mole of I disappearing(or uice uersa). Finally, we note that Eq. l8.l-12
becomes
(V.u * ):
j1(R r
0p,, ,
; r r P- t ( V'u) f ( u
ot
* R r:)
(r8 . 1 -1 3 )
+ e.yc,)
U:!
0r,n
i c_r ( V' u*) * ( u
0t
C h a nge f or Mult i c o m P o n e n t
S y ste m s
tmponent B rs
B ):
rB
(18.1-7)
S 57
(l 8.1-8)
P u) : 0
( 18.1-e)
=0
vr) : R'r
( 18.1-10)
(v'
R,,
'fi * Co'c,p*'): c9,,,flr,)1
( 18.l- 14)
( 18. 1- 15)
Vr):
Rn
( 18.1-1r)
op,t
* r.a
+ pj(v' u) * (u'Vp-r) : (y',.,,fl)p1
0t
(18.116)
( I 8.1 -l 2 )
R1+ Rr)
(18.1-13)
* R,1
* rr.Vc,) : !y',,,P2c,n
(18.1-17)
vr - t
At
(18'1-18)
Bu t ac c or dingt o Eq . 1 8 .1 1 3 , (V ' r* )
Henc eE q. 18. 1-1 8b e c o m e s l
u;*t*.vcr):91pv2c,1
S ystems
+.(+.ry
Cy Iindr ical coordinates :
TAE
(
THE EQUATIONOF CONTINUITY
(Eq
" .4 :
q ,,,v z c ,
(18.1-20)
OT
+ . (:l{'*u,t
Spher ical coordinates :
+ . (i,'!,{"*n
^,*
TI
Rectangular coordinates.
o
dc.t
1c,t
0c,
- . + fI u .- :j
+L 'z* u-,- :
oA
d
t
at
\*
OF A
$r 8. 2 T HE E QU AT ION OF C O N T T N U T T Y
I N CUR V IL IN E ARC OOR D IN AT E S
in this sectionthe most important equationsgivenin $18.1are summarized
in rectangular,cylindrical, and sphericalcoordinates. They are tabulated
for ready referencein setting up problems. In Table 18.2-l we give the
equati<inof continuity in terms of N;, and in Table 18.2-2, the diffusion
*,
* * (,,#*,,'r#
lla
= r t ; n\ ,
molecularweight:
A
; ln M + ( u. V ln M ) : 9noYz
ln M
(18.1-l9a)
0,
by C. H.
in which M : reMt * tnM* This relationseemsto have been first suggested
Bedingfield,
Jr., and T. B. Drew, Ind. Eng. Chem.,42,1164(1950).
'?By equimolar counter-diffusion,we mean that the total molar flux with resPectto
stationarycoordinatesis zero.
3 J. Crank, The Mathematicsof Difusion, Oxford UniversityPress(1956).
aH. S. Carslawand J. C. Jaeger,Heat Conductionin Solids,Oxford UniversityPress
(1959),SecondEdition.
Spherical coordinates :
*,,i**
T *(,,,*
:
.,
S yste m s
i n C urvi l i near
s59
C oordi nates
TABLEI8.2-I
canbe replaced
by (llc)(R" * Rr).
TH E E Q U A T I o N o F C o N T I N U I T Y o F A | N V A R | o U s c o o R D | N A T E S Y S TEM S
(Eq. l8.l-10)
r *R-r -!(n-,
* R,u) (18.1-19)
c
'nsttj gasesat constant temperature
atlon cannot be written as Dc,,f Dt
of u.
Rectangular coordinates :
lt *(u*n,
at'\a'
(A)
+dN,t, *'Tr'\:n,
arl
oy
Cylindrical coordinates:
E qs. 18 .1 -1 4a nd 15 t hat m u s t b e
hangesoccurring, then r_r, rp, Ra,
z er oin Eq . l 8 .l - 17 or if u* is z e roi n
u r ^*( ,- 1 ,,' ^ ,_ ,+ 1 3 +
: n,
1 49Als\
t
'
'" '4 "
d0
At
\r ar
(B)
Spherical coordinat es :
,Y'r-o
(18.1-20)
: R.r(c)
0)*
]r*u,sin
?)
+ . $-|r**u,t.
-h
-,*
TABLE I8.2-2
T H E E Q U A T I O NO F C O N T I N U I T YO F A F O R C O N S T A N T p A ND 9 1 '
(Eq. l8.l-17)
Rectangular coordinates:
* *(,.**,,**,"+):'^"(#.# . +) * oio,
J I T Y OF A
rEs
t ionsgiv e ni n $ 18. 1ar e s um m a ri z e d
.l coordinates. They are tabulated
ems. In Table 18.2-l we give the
and in Table 18.2-| the diffusion
.,"+)
* *(,,#*,,!,+
: '^"('l*'(:#
).'}#.#)*^ ^ (B )
. l- 19 can be writ t e n i n t e r m s o f u r a th e r
tion, namely the logarithm of the mean
t : 9 t f l zl n M
( 1 8 . 1 _ l9 a )
press
Spherical coordinates:
dc,
dc,,
ldcs
,* "rink)
I
* l,'. a, + ''o; au
^ ll
: _rtt\7
a/,ac-1\
* \,' E
)
.#**(""'+).^k
#).t,
560
S ystems
i:1,2,"',n
Dt
..a
(18.3-1)
generallyneedscxplicit expressio
gradients and the transport coeffi
cientsalso needto be known as fu
It has been pointed out in prece
changetha t t heseequat ionsm ay as
ing on (a) whether DlDt or 0l0t is
for the fluxes,(c) whether masso
various forms of energy are broke
For example, we may rewrite E<
(moti on)
-p i (Y.u ) - (V .i o ) * rn
p+:
'
of Change in Terms of th
Equations
-[V
.* ] * Zp, E ,
- ' ilr
(18.3-2)
Here we have introduced for the sake of brevity the pressure tensor zr :
r * p6' in which r is the viscous part of the momentum flux (or shear
stresstensor),p is the static pressure,and 6 is the unit tensor. Note that
Eq. 18.3 2 differs from the equation of motion for a pure fluid (Eq.3.2-10)
only in the last term, where p! has been replaced,by Dprgr. In ihat term
accountis taken of the fact that eachchemicalspeciespresentmay be acted
on by a differentexternalforce per unit massg,.
(iii) The equationof energyfor the mixture:
- ( V'
{p, u*
fr0,:-[v'{pu
a^
(energy) ! p{0 * lu'} : -('
ot
+ i @,' l ' n
t=l
P@iu+,
g: puu*t
e:
p{0 I
(continuity)
lp,:-(!
0t
.a
(moti on)
"pu: - [ \
0t
(energy.)
+;,
!o t p1o
For one-dimensionalsteady-sta
external forces the fluxes n,, S, at
particularlyconvenientfor setting
masstransfer. (SeeExample18.5
7
The Equations of Change for Mutticomponent Systems
TABLE I8.3-I
THE EQU ATI O NO F ENERG YFoR M ULTIC o M P o N E N Ts Y s T E M s o
InTerrnsof
E:
p
O + fr +a:
(exactonlyfor
a6/ar:O)
DEn
: -(v .q) - (v .[n . u])+
Dt
.Z7r..g)
(A)
InTerrnsofO+fr:O+$u2:
Dr,
e .(U
(ni.E)
(B)
In Termso1fr : !u2:
DK
:
' Dt
p: p+?rl^.r-
-(u . [v .rr]) * |
ci@ . Ei)
(c)
In Termsof 0:
n
DO
P Dt : -(V .el - Gc:Vu) * >(jt.C)
(D)
i:7
in which ( : -0ld(0pl1x),
is
indicateshow much the density
motion then becomes,for gravity
In Terms of fu:
DH
: -(v.s)
' Dt
Dp,
(E)
In Termsof Co:
^DT
_
'oc^
' Dt
/:r^
ii
\d
I'/pn
2
Dt
.J,) - Ril
+ ) -tr,t<v
(r)b
In Terntsof e u:
^DT
_ : -(v .q) 'oc^.
" Dt
In Terms of Ei:
\" r /e,r ,/
a p \ -f
* ilo,* lp/\ - r "'/
4lttv . J i) - n , 1
^ -f _)
) ,o .,
(c )
* ("'i*a) :o'kvr)
*(,2,"'n')
. ' # - ( r : vu )+ i{ in .s,)
Da_
_:
:
p
'Dt
_[ V. "]
" See $18.4 for the definition ofthe heat fluxes in these equations.
o L. B. Rothfcld,
personal communication.
c The usually unimportant Dufour
energy flux g(r) has been neglected here
554
S ystems
_p(yu
gradi
Velocity
Fluxes
Momentum
(second
order
tensor)
Newton's
law
Itt,xl
Energy
(vector)
Mass
(vector)
r Two articlesdealingspecifical
energyfluxesare J. G. Kirkwoodar
(1952)andR. B. Bird,C. F. Curtis
. (
S ez' es,
No. 16, 51, 6985( 1955)M
-5--
C h ange f or Mult i c o m p o n e n t
S yste m s
F luxes i n Terms of Transport
P roperti es
565
thermodynamicsand the transport processeswill find several suitable referenosin the literature.l
The expressionsfor the momentumfux r in Chapter 3 are valid for
mixtures as well as for pure substances.For Newtonian fluids r is a second
order tensor given bv
(18.,t-1)
gradient
Temperature
Fluxes
Momentum
(second
ordertensor)
gradient
Concentration
gradient
Pressure
External
forcedifferences
Newton's
law
l P , xl
Energy
(vector)
Fourier's
law
Mass
(vector)
Soretetfect
lD,{rl
Ikl
Dufour
effect
r atun
I r
I
Fick's
law
lDAE l
F ig. !8.G1. S chemati cdi agram show i ng roughl y the rel ati ons betw een fl uxes and dri v i ng
fo r ces i n a bi nary system. The associ atedtransport coeffi ci entsare show n wi thi n brac k ets .
56 6
S ystems
(18.4-2)
(18.4-3)
Here ,9, is the partial molal enthalpy of the ith species.The Dufour energy
flux qt ' t is quit e c o m p l e xi n n a tu rea n d i s u s u a ll yof mi nor i mportance;hence
it is not further discussedhere.2The radiant energyflux gl'r may be handled
s epar at elyas de s c ri b e di n 8 1 4 .6 .
Frequently it is desirableto usethe energyflux with respectto stationary
c oor dinat ese,
, ra th e r th a n q . By u s i n g th e d e fi ni ti onof e, E q. 18.3-9,and
the foregoingexpressionfor q, we may write
i, : i!') -
e : _kV T +>F,t, * p u * p Uu
I:f
?2n
ii"):'
tM,M,
pRT Fr
il,)-'
\M,M,
PRTi=t
^2n
jlo':-4i*,
pRT Ft
(1g.4-4)
Wher rq( ' ) , [ r ' u] . a n d (!rp u ' )ua re o f n e g l i g i b lei mportance,w e may approxi mate e as
: -kvT+iE,t, +ir,fr,,
Fl uxes i n Terms
i: ') :
- Dir v
hT
In theseequationsG, and V, ar
energy) and volume, respectiv
coefficients,and the Drr are mu
The D,, and Dor have the follo'
Du:
(18.4-5)
iItI
i{*,*
i=1
e : _kvT +: N, 4
(18.4-6)
.:l
r
C h ange f or M ulti c o m p o n e n t
S yste m s
or diffusion-thermoeffect. We may
tive to the massaveragevelocity
1{a)q q&\
(r8.4-2)
:28, J ,
(18.4-3)
i=l
n.ul * p { C + tr u,}a
( 18.4-4)
ligible
importancc,
we mayapproxi-
F luxes i n Terms
of the Transport
S O7
(r8.4-7)
v*-l
i:',: +
f ,,*,r,,lr,i (?9)
p,.t i=1
toru,T:;:r,
(18.4-8)
t\": # t,r,*,o,,1",*,(#,:)"r]
(r8.4-e)
L f;j
- 2,f t,)f
i:": - # 2,r,r,o,,12,r4,(t,
(r8.4-ro)
i:') : - Dirv l\ T
(18.4-11)
In theseequations G, and v, are the partial molal free enthalpy (Gibbs free
energy) and volume, respectively. The D, are multicomponent diffusion
coefficients,and the Drr are multicomponentthermal diffuiion coelicients.
The Dn, and Drr have the following pioperties:
,J,{ pu * pUu
.ri J p nu
Dii: o;
J, + l c , H , u
P roperti es
(18.+5)
2 r n' : o
(18.4-r2)
i:l
(18.4-13)
i =7
(18.4-6)
5 68
S ystems
Fluxes in Terms
of the Transport
Prope
1 8 . 4 -r.
TABLE
E X PER IM EN TAL
TH ER M ALD IF
Bi n a rySy s t em s
AND LOW.DE
_t)orl' l _ D-1rv
- p!:G, - sa)
tn r
" * e
' M .t
(18.4_14)
P
Pt
T hi se q u at ionm ay be w ri tte n i n a n a l te rn a tefo rm b y usi ng (dGr)r,r:
RTdln a l and by dcfining6a "thermal diffusion ratio" hr:
(D
D.1B ) :
"rf
/^2,
f/:
r-
(pfc2M,aM) x
-l
Mro t,t,
M , r , lV,
l\ t E . t - E t,) + --_ " 1 :-._ ' _ _ l v p + AzV l n T | (18.4 15)
pRT
R T ' M.,
p'
I
This equationis the startingpoint for the study of ordinary,forced,pressure,
a Separations by thermal diffusion may be
considerably enhanced by combining the
eff ec t wit h f r e e c o n v e c t i o n i n a systcm sim ila r to th a t sh o wn in Fi g.9.9-1. A col umn
that makcs use of thesc two effects is callcd a Clusius-Dickel column. Such columns have
b een us c d f o r i s o t o p e s e p a r atio n s a n d fo r se p a r a tin g co m p le x mi xtures of very si mi l ar
organic c om p o u n d s . A v e r y r e a d a b le in tr o d u ctio n to th e r m a l d iffusi on i s the smal l book
by K. E. Grew and T. L. Ibbs, Thernnl DilJilsion in Gases, Cambridge University Prcss
(1 952). F or a p p l i c a t i o n s t o l iq u id s, se e A. L . Jo n e s a n d R. W. F oreman, Ind. E ng. C hcnt.,
44, 2249-22 5 3 ,( 1 9 5 2 ) , a n d A . L.Jo n e sa n d E.C.M ilb e r g cr ,
In d .Eryg.C hen.,45,2689-2696
(1953). The m a t h e m a t i c a l t h e o r y o f th e th e r m a l d iffu sio n co lu m n i s descri bedi n a cl assi c
article by R. C. Jones and W. H. Furry, Reu. Mod. Phys.,18, 151-224(1946).
5 Not e t h a t t h e q u a n t i t y i n th e sq u a r e b r a cke ts h a s
th e d im cnsi ons of force pcr uni t
mas s ; hence l c t r l s d e s i g n a t eitb y - F ,4 . Wh e n th e r e la tio n s in T abl e 16.1-3 arc used,one
can show that Eq. 18.4-14 (omitting the thermal diffusion tcrm) becomcs
D^"!l:F^
Components
A -B
T( "K)
C2H2Cln-z-CuHra
CrHnBrr-CrHoCl,
c2H2cl4-cc14
CBrn-CCln
ccl4-cH3oH
cH3oH-H2O
cyclo-CuHrr-CuH.
298
298
298
298
313
313
313
kr
no
0.5
1.0
0.5
0.22
0.5
0.06
0.09 0.12
0. 5
t . 23
0. 5 - 0. 13
0. 5
0.10
^
j . , : _jn : _ l, t ,l M . rMu D .,,,.
,
IL\ld::"ln ". r,. otI r . ,vr_
p
,
tt - u* :
^Rr
Liquids"
: ntnsFu
(18.4-14a)
(1e56).
bAbstractedfrom tablesgivenby J. O
^2\
j e: _l | l uouu
\ p/
This should be compared with Eq. E ir
/.2\
i ", t : - l : - l U "\ p/
jr:"_ lMrnt,nnpr
P i=r
C ha ng e for M ult i c o m p o n e n t
S y s te m s
steeptemperaturegradientsso that
:hephysicalaspectsof thesegeneral
ing cases.
le #,),,
L \0r.,,
- 1)orl
-J p/
Vr',
D4rv \n T
(18.4-14)
(plczM.rM6) x
"" I v.r,
*A' T,P
t\
I
- -lvp * k7v In T |
o'
(18.415)
studyof ordinary,forced,pressure,
:onsiderably enhanced by combining the
t o t hat s hown in F i g . 9 . 9 - 1 . A c olu m n
lusius-Dickel coluntn. Such columns have
L r at i ngcom plc x m i x t u r e s o f v e r y s im ila r
o n t o th erm al dif f u s i o n i s t h e s m a l l b o o k
on in Gases, Cambridge Univcrsity Press
nes and R. W. Foreman, Ind. Eng. Chcnt.,
Milberger, Ind. Eng. Chenr.,45,2689 2696
diffusion column is dcscribed in a classic
o d . Phys. , 18, l5l-2 2 4 ( 1 9 4 6 ) .
)ts has the dimensions of force per unit
t h e r el a ti o nsin T ab l e l 6 . l - 3 a r e u s e d , o n e
I diffusion term) becomcs
--3 : iltnFt
Q8.4 14a)
a l ion wa s us c d in t g . 1 6 . 5 I i n c o n n ectio n
are the thernnl dilfusion factor a and the
or nzuT
(1 8.4 l5a)
a t io n fo r g as es ; t hc q u a n t i t y o i s g e n e r a lly
B eca usel, is det i n e d i n l e r m s o f Dr r ,
he colder region; when k" is ncgative,
Fluxes in Terms
of the Transport
Properties
569
nn
T(K )
C2H2Cla-n-CuH1a
CrHrBrr-CrHnCl,
c2H2cl4-ccl4
CBrn-CClo
ccl4-cH3oH
cHsoH-H2O
cyclo-CoH12-CsHo
298
298
298
298
313
3l 3
313
Components
A - B
r(' K )
kr
0.5
1.08
0.5
0.225
0.5
0.060
0.09
0.t29
0.5
t.2f
0.5 -0.1 37
0.5
0.100
Ne-He
Nz-Hz
Dr-H,
kr
oa
330 0.20
0.60
2@ o.294
0.775
327 0. 10
0.50
0.90
0.0531
0.1004
0.0548
0.0663
0. 0145
0.0432
0.0166
u
ie : - (!\
\ p/
\d ln x^/r.,
^,,t"r,'(+llo)
Y,n
(18.4-16)
/ ^2\
\:- )tvt
(18.4-17)
eu eO aBV rA
jr :"
i*n*,r ,pr n
P i =L
i:1,2,"
,n
(18.4-18)
S ystems
V ', - 2 : + ( u , - u , ) : i - t
rhese
equari.",
",..-i""T'
^,*"'|ri;t,.f;,':.:r:";^:^":.;", ,l
-c?tn\
this analogousrr
Ni:
- cQ
2. 5
p Da B
2.0
I
--=cUr,,
trl
1. 5
rtDtn
lnL
--0
1.0
9,,
Mole fractionether
Fig. 18 . # 2 . E f f e c to f a c tivity o n th e p r o d u ct o f visco sitya n d di ffusi vi tyforl i qui d mi xturesof
c hlorof o r m a n d e t h e r . [ F r o m R. E. Po we ll,W. L . Ro se ve a r ea, n d H enry E yri ng,tnd.E ng.chem.
3 3 ,4 30- 43s
( t e4t ) . 1
is the 9 n, tfrat appear here rather than the Do, and that the g
r, are virtually
independentof composition. (See Eq. 16.4-13.) This is the usual starting
? C. F . Cur t is s andJ .O.H i rs c h fe l d e r,J .C h e m .p h ys.,17,550-555(1949).
Forathree_
component system, the relations are of the form
o,,:
'-
c,,[t
' "1
xsl( M xtM ) 2 !3
- 2 n)\
r r ? zt * r z? r t * t"?rr|
(18.4-18a)
i han ge fo r M ult ic o m p o n e n t
Systems
. t c y/
t r,l g , - r ; N, )
( 18. 4 -1 9 )
ij
571
j.
:
.-,
P roperti es
-c9,trrY*t
(18.4-20)
* tl(N,r * Nrr)
by this analogousrelation:
(r8.4-21)
Nt: -c7i,,Vr, * t, I N,
1
CQi,n
2r(11c9)(,Ii-,,N
rl
':/
N, -
(r8.4-22)
tL - - )
'N
ether
; cosi tyanddif f us iv i t yf o r l i q u i d m i x t u r eso f
s eve are,
a nd Henry E y r i n g ,l n d . E n g .Ch e m .
(18.4-l8a)
D "r '
)ressure, thermal, and forced diffusion,
r (loc. cit.); see also J. O. HirschfelJer,
of Gases and Liquids, Wiley, New York
9i t
(18.4-23)
9"
(18.4-24)
tsz',/ r,
( 18.4-2s)
the assumptionof
ln systemsin which the variation of I i* is considerable,
has
proven
useful.r0 The
distance
linear variation with composition or
e The systcmatic use of an effective binary diffusivity seems first to have been suggested
by O. A. Hougen and K. M. Watson, Chentical Process Principles, Vol. III, Wiley, New
York(1947),pp.917-979. Methodsofeval uati ng9;-forspeci al caseshavebeendev el oped
b y C . R . Wrl ke, C hem. E ng. P rog.,46,95-104 (1950) and W. E . S tew a rt, N A C -A Tec h.
Note 3208 (1954.
10H. W. Hsu and R. B. Bird, A.I.C'h.E. Journal (in press).
s72
S ystems
$18. 5 US E O F EQU AT T ON SO F C H AN G E TO S E T U p
DI F F US IO NPR O B L EMS
All of the problems of Chapter 17, and more difficult ones as well, may
be set up directly by means of the differential equationsin this chapter.
As exampleswe considercombinedheatand masstransfer,thermal,pressure,
and forced diffusion,and three-componentordinary diffusion.
Exa mple
o
o
l
Heat a n d M a s s T r a n s f e r
d-
N s" =
Insertion of Eq. 18.5-3 into Eq. I
profiles
( t- 'o
\r - ,r,
C h a nge f or M ult ic o m p o n e n t
S y ste m s
573
continuity and energy for this system. Thesc may be written from Eqs. 18. 3l0
an d 1 2 a s
(continuity
of .4)
: t
(energy)
( 18. 5- 1)
*dz :,
(l 8.5-2)
the film.
.-A
--n
T
=7 .
--0
Jr = rr^
7 T =T o
t o =, o t
B oundaryof
gas fi l m
.NGE T O SET UP
Directionof movement
A
e
of condensablvapor
o
o
l
!
a
J
Fig. 18.5-1. Condensation
of hot vaporA on a cold surfacein the presence
of a nonconde n s a b lgea s8 .
To determine the concentrationprofilc, we need the mass flux for diffusion of I
through stagnantB:
j^,
v 'tt
C ?,1 6
| -
. |
d.r - 1
{ t d ' )-J )
,t,
l'
-l
\r -
r.
/,10./
/l
: l;
\t -
,'
\?/d
r,,_
r u,. /, !
r r 8 .5 ,4 )
* n, : ' #r "*
( 18. 5- 5)
574
S ystems
Note that N.1, is negativein Fig. 18.5 1 becausez1 is condensing. The last two
exprcssionsmay be combined to put the concentrationprofilesin an alternateform:
t l' . 1rjrd-
t 1.
1o,
ex pl( Nt r lc o t t ) z l
_1:r_{o 1 - exp [(.N,rrlclu)6]
(18.56)
jy) : -:
To determine lhc tctnperatureproJilc, we use the energy flux from Eq. 18.4-6
for an ideal gas:
-k
_l
o:j'n+jtl):
dT
,
+ lHjN4 ,+ HBNRz\
Thi s bul b mai ntai ned
ut
-k _ * N _ ,rc ,-r{
T-
To)
(18.5-7)
Here rve havc chosen 7o as the rcfcrence temperature for the enthalpy. Insertion
of this exprcssionfor c, into Ec1.18.5 2 and integration betweenthe limits T : To
at : : 0 and I : T6 at z : r) gives
(r 8.5-8)
It can be seenthat the temperatureprofile is not linear for this systcmcxccpt in the
linrit as N,1,C,,,a lk 0. Not c t hc s inr ilar it ybet weenE q s . 1 8 . 5 6 a n d 8 .
The conduction energyflux at the wall is greaterhere than in the absenceof mass
transfer. Thus, using a superscriptzero to indicate conditions in the absenceof
mass transfer, wc may write
- k(dTldz), o
- kktwtt-,
(N.l,e
D.tlk),5
( 18.5-9)
xs2- fia
Becausethe dependenceof k7 on 7is
k? constant at some mean temperat
approximately
r A2 - n
Di f f u s i o n
Considcr two bulbs joined by an insulatcdtube of small diametcr and filled with
a mixture of ideal gasesI and B as shown in Fig. 18.5 2. The bulbs are maintained
at constanttemperaturesof f, and ?"r,rcspectively,
and the diameterof thc insulated
tubc is snrall enough to eliminate convection currents substantially. Develop an
expressionfor the steady-statediffercncein composition of the two bulbs.
So lutio n. Acco rding t o Eq. 18. 4 15, t he t em per at u r eg r a d i e n ti n t h e s y s t c mw i l l
causea mass flux given by
(18.5-r0)
Exa m p l e 1 8 .5
This mass flux will tend to establisha concentrationgradient, which in turn will
result in an opposedflux:
s'
c2
)l (NA , l c a])zl
t[(N,a,lct111)d)
(18'5-6)
575
i9 : - 7 *or o"onT
( 18.5- 1r )
When steady state is reached, there will be no net mass flux and we may write
o : i',t)
+j'I) : -! u ,rr" ,r\* .+n
u85 12)
,{A, + frBNR,)
Thi s bul b mai ntarned
:rA(T-
To)
(r8.5-7)
(r8.5-8)
not line;rr for this system except ir.rthe
be t w e e nE qs. 18.5-6 an d 8 .
reaterherethan in the absenceof mass
indicateconditions in the absenceof
(NA , et , Al k)i
tf-ry,,,f'",/t),ll
"p
( r 8.s9)
Jirectlyaffectedby simultaneousmass
ffusion)the mass flux is not directly
any applications,for exanrplcin most
, a n d t he right sid c of Eq. 18 .5- 9 is
: relationshipsbct'nveenheat and mass
kr dr
( I 8 .5 * 1 3 )
' t":- TE
In general, the degree of separation in an apparatus of the kind being considered
is small. We may therefore ignore the effect of composition on k7 and integrate
Eq . 1 8 . 5 1 3 t o o b t a i n
fr, k, ,_
xA2-xAt:-|,".
( r 8.5-1
4)
io,
!
r7
( l 8. 5-15)
k rd r
.
R - , 1R T E
( 18. 5 -1 0 )
T,^:
TrT,
,:jrln
T2
7,
( 18. 5l6)
576
short with respect to the radius of rotation Ro, and the solution density may be
considereda function of composition only. Detcrmine the distribution of the two
components at stcady state in terms of their partial molal volumes,position in the
cell, and the pressuregradient dpldz : - pgt> -pO2R0 in which O is the angular
velocity of the centrifuge. Neglect changes in the partial molal volumes with
composition and assumethat the activity coefficientsare constantover the range of
compositionsexisting in the cell.
of Change
Exam ple 18
A quiescentaqueoussolutionof
plates of metallic M, as shownin F
between the plates under such co
dissolutionof the anodeand deDos
tration profileof MX in the solut
Cathodeof
metal l i cM
(M- + e--M)
\\"0/
\\/
\
\
Use of Equations
\/\,,
ll)
I
I
F
I
tl
rl
Mixtureof A and B
in d iffusi oncel l
At steady state the net mass flux j4, is zero, and we may write Eq.
d
t-
rrr4J
-(#)
di stri buti on
( r 8.5-l7)
- /"M)H)
(#) "(#)'-': "*o(rzo,'rn
1 8 . 5 - 1 8 d e s c r i b e s th e ste a d y- sta te co n ce n tr a tion
,n/
Fig. 18.5-{. {
(M,a-pv,1)
E q.
xu*
trsr-,sl
for
a bi nary
r:N,r
0:Nr
Use of Equations
sTl
of Change
I Motion
I
Cathodeof
metal l i cM
Anodeof
metal l i cM
(MM'+
(Mr +e--M)
r+
tz l
oIe
e-)
ll
ll
!<-
r,
+l
Mixtureof A and B
e n t r i fuge. The m ix t u r e o f A a n d I t e nd s to
r ce di n the c ent rif u g e .
l ux T_ a,i s z ero, an d w e m a y w r i t e Eq .
ozL
Fig. 18.5'{. Concentration
polarization.
(Mt
( 18. 5t7 )
p/,)
' oM o -
9n;
V "M .'
' '1RTI
";:=l
"
(18 .5 l8)
:gration.A development
of Eq. 18.5-17
\. Guggenheim,Thermodlnoniics,North
35G360. Note, however,that Guggenbraicerrorin the third line of Eq.1I . l0 3.
Assume the solutions to be quite dilute and ignore changes of temperature and
physical properties.
Solution. We may consider the solution in this apparatus as a ternary mixture
of water and the two ionic speciesM+ and X-. lt can be seen from the electrode
reactions that Nly*, the magnitude of the molar flux of M+ , is proportional to the
current density in the cell and that the fluxes of X- and water are zero. It can be
further seen that the local molar concentrations of M+ and X- must always be
eqrtal by the requirement of electrical neutrality. Finally, since the solution is
dilute, we may consider that the fluxes N,. and Jr* are equal.
We mav immediatelv write
r : Ny+
t!|ft
=
Ji
bt
0:N x-
+ J#l\
(r8.5-r
e)
(r8.5-20)
* rl l or
as equivalentsper unit area
Here I is the currentdensityin the solution,expressed
s76
S ystems
short with respect to the radius of rotation Ro, and the solution density may be
considereda function of composition only. Determine the distribution of the two
components at steadystate in terms of their partial molal volumes, position in the
-pO2R0 in which O is the angular
cell, and the pressuregradient dpldz : - pgg
velocity of the centrifuge. Neglect changes in the partial molal volumes with
composition and assumethat the activity coefficientsare constantover the range of
compositionsexisting in the cell.
fto
r\/
.,
\/t-
of Change
Exam ple I
A quiescentaqueoussolutionol
platesof metallicM, as shownin
betweenthe plates under suchc(
dissolutionof the anodeanddepo
tration profile of MX in the solu
\
(M-
V',
If---12=
Use of Equations
Cathodeof
metal l i cM
+ e--M)
i-r'
F
I
,il
lVixtureof A and B
ll
rl
-l
L
0
At steady state the net mass flux7.1" is zero, and we may write Eq.
d
; ln. r r :
(r8.5r7)
ru+ fI
xn 7
di stri buti on
t,u,-',;
for
a bi nary
Fig. 18.5-{.
Use of Equations
s77
of Change
Cathodeof
metal l i cM
(M- + e--M)
I c entri fu ge.The m i x t u r e o f A a n d 8 t e n d s to
d u c ed i n t he c ent ri f u g e .
ozL
Fig. 18.5-1. Concentrationpolarization.
iltu.,-
pl.,l
o8.5 17)
ileMn - v"M^)Yr)
( I 8 .5 -t8 )
r t eg ra ti o n. A dev e l o p m e n t o f E q . 18 .5 - 1 7
A. Guggcnheim, Thermodynanrcs, North
rp. 35G360. Note, however, that Guggeng e bra i cerror in t he t h i r d l i n e o f E q . l l.l0 3 .
Assume the solutions to be quite dilute and ignore changes of temperature and
physical properties.
Solution. We may consider the solution in this apparatus as a ternary mixture
of water and the two ionic species M+ ar,d X-. lt can be seen from the electrode
reactions that Nr11',the magnitude of the molar flux of M+, is proportional to the
current density in the cell and that the fluxes of X- and water are zero. It can be
further seen that the local molar concentrations of M+ and X- must always be
equal by the requirement of electrical neutrality. Finally, since the solution is
dilute, we may consider that the fluxes N; and Jr* are equal.
We mav immediatelv write
1 : N , 1 1 +=J i ; i t +J i ; t l
0:Nx-
'Jtr?t *tfit:t
(18.s-19)
(l 8.5-20)
fr-'
578
S ystems
per unit time. To expressEqs. 18.5-19 and 20 in terms of the transport coefficients,
we must make some further assumptions. We assume that the M+ and X- ions
are in such small concentration as to have no appreciable effect on one another.
Then we considereach ion as diffusing in a binary systemwith water as the second
component. We further assume the activity coefficients of the ions to be unity.
Then dGi : RT dlne, and for the ionsErz : Gilm)( -d6ldz). Here { is the local
electrostaticpotential, er is the ionic charge, and mi is the ionic mass. We may then
write Eq. 18.4-15 for ionic speciesI diffusing through water (w) as
Ji"*: -rr*(9*.##)
ko "
(18.5-2
l)
By substituting
Eq. 18.5-21into Eqs. 18.5-19and 20,we obtain
ru:_ce1**(ry
.+#)
o:_csx_w(+-+#)
(r8.5-22)
( 18.5-23)
We now take advantage of the fact that the mole fractions of the two ions are the
same to eliminate the potential gradient between these two equations:
[r:
dr n",
-2 c ? u * r-i -
(18.5-24)
rAd =
Since for dilute isothermal solutions the quantity cQM*, is nearly constant, we may
integrateEq. 18.5-24to obtain
rM+-ro__
I"
2 c9 tr 1+,
(r8.5-2s)
4 C? y+ *x^ u .
L
**:.,"('-,
(18.5-26)
dto
Y l ,,n
aL
---;
:("-;)
rn(
We now subs
Here R -- ro - lln).
integrate the resulting first-order linear
ra : (ras-
N r + M-1.us6)exp (N
(r8.s-27)
HereN:(1
-rr)and
M :1 - n
Y
C h an ge f or Mul t i c o m p o n e n t
S yste m s
aC1
1,
'z * "t.t
( l 8 .5 -2 1 )
(r8.s-22)
xT dzf
E)
"r
_ '"-1.'i4\
579
ktr"*rh
atz
( l 8. 5- 28)
:6
Here kn" and I are constants assumedto be known. Develop an expression for the
reaction rate in terms of the gas composition at z : 0. Assume constant temperature and pressure and ideal-gas behavior.
--l
( I 8.5-23)
KT d rl
mole fractionsof the tw, ions are the
weenthesetwo equationsl
dty+
'r-A;
(r8.s-24)
'a nn
K
-;;-
I,
LLZM+w
(l 8.5-25)
thode.
:nt in the cell is linear. The maximum
:oncentration at the cathode is zero:
W+wravg
Fi g. 18.5-5. D i ffusi on ofA through stagnant8 to form A " at a catal ytics url ac e.
( I 8.5-26)
ralitativedescription of "concentration
e applicationis limited to quite dilute
rat in an electroplating bath there is a
teposited. Similarly, in a battery the
ch current can be drawn.
I
\J'
/
\
,./
dru
: /
,t(
\' o-
1\
il''o
zl 6,51G524 (1960).
* (.ra,-
rs)rq- ra*
( l 8. 5- 2e)
( 18. 530)
l\
-;l * t
rBoexp (Rrl.,iro
( 1 8 .5 3 1 )
( l 8.5-27)
Her e N : ( l - n - 1 )
and M:l-
nll(l-
M - 'r 3 r , e x p ( R r . r , r 0
rs,,)l?r-
( 1 8 .5 - 3 2 )
r 1 , , ) ) . F i n al l y, w e u se
580
^JaF:(r.ro-
N 1 + M lrps)exp(Nr,a,u.rp)
+ N-r - M-1r30exp(Rr,_r,.n)(19.5_33)
(v'u ) : o
(continuity)
Dxj
(continuity of ,4)
DI
(r8 . 6 -1 )
: !1 ,,,v z r ,
/l R 6-)l
fo rcetl
(motion
p : uv'u*{_oJr**,,0t_
I
ff
rn)
(18.6-3)
(18.6-4)
d i m e n s i o n l c svse l o c i ty
p*
' :
P 1.
: d i rn e n s i o n l c spsr essure
( r 8.6-5)
.P ;'
pv"
Vt
t * - i --: : d i me n s i o n l e stisme
D
r'r* :
(18.6-6)
dimensiolrless
concentration
(1s.6-'7)
tffrr:
5 F o r t h c s p e c i a l ca se s, n :1 ,
Bird, op. cit.
r 1 n :r r ,
a n d ( n r 3 -1):ru(n
(v
(continuity)
(continuity of ,4)
DrA*
l ), see H su ancl
Dt*
(motion)
(v
(continuity)
J ree
i n whic h r r o is s o m ere fe re n c e
c o n c e n tra ti o n .In E q. 18.6 3 w e have w ri tten
the equationof motion to includeeither the forced-or free-conrcctionterms.
we first considerforced conrectiotlfor which it is convenientto define
th e r educ edqua n ti ti e smu c h a s i n Q1 0 .6 :
o* : !.:
t/
D i mensi onal
2g
(continuityof .4)
(moti on)
Dl**
Du**
Dt**
i n w hi ch G r ut :
pz( gD3( r ut transfer. We see that Grrn diff
(@n, - rro), whereasGr contain
In C hapt er2l use is m adeof t l
c
the correlation of mass-transfer
ment exactly parallelsthat for he
the dissipationfunction, the corre
the same. We may thereforeexp
heat and masstransfer. Howeve
gies cannot be fully understoodw
onp,a, Z, and ro. Thestudentwi
Dimensi onal
Nr7 1,p)
^u
N-t - M-lrrts exp (Rr,_1,7;)(18.5,33)
.5 33 g i vesr_r"r :ts a n implicit func t ion
TH E E Q UA T I ONS OF CHANG E
- F L U I D MIX T URE
sedthe equations ofchange for a fluid
i l to s e t up and solve some p rob lem s
:ns i o n a lanalysis of th c eq ua tions f or
constant viscosity p, and constant
the r a n ge of com p osition to b c s m all
rl a r de n sity c are cssen tially co ns t ant .
l at i o n s of chang e a s
:0
(r8.6-t)
,ttvzr,r
( 18.62)
-t pg
forced
( 18.6*3)
( 18.64)
velocity
nlesspressure
( 18.6s)
s time
( r 8.6-6)
l):
rn ^ Q t -
D rA *
(continuity of ,4)
(motion)
( 18. 6- 8)
(continuity)
Dt*
Du*
Dt*
g* rr" *
(18.6-e)
Re Sc
1 g * t r*
v x^p * *
Re
+Lg
Ftg
(18.6-10)
(e_r-
Jree
":n)
rti on. I n Eq . 1 8. 6- 3wc hav e w ri tte n
t he f orce d -o r free- c onv ec t ion
te rms .
b r w hich i t i s c onv enientt o d e fi n e
581
(continuity of l)
(motion)
(18.6-1
1)
(V * ' u* * ) : Q
D r,t*
Dt**
I g* zr" *
(18.6-12)
Sc
D'** :v*2u**
Dt**
xA* Gt,ru9
(18.6-13)
C'
o
in which Grtn:
p2(gD\(xnr- r',)l 1"" is the Grashof number for mass
transfer. We see that G1173differs from Gr only in that Gry6 contains
t@n - oro), whereasGr containsfr(T, - Tl.
In Chapter 2l use is made of the groups Sc and Grr' in connectionwith
the correlation of mass-transfercoefficients.Note that the foregoing treatment exactlyparallelsthat for heat transferand that, with the exceptionof
the dissipationfunction, the correspondingequationsin the two sectionsare
the same. We may thereforeexpect to find many close analogiesbetween
heat and masstransfer. However,the extent and limitations of theseanalogiescannot be fully understoodwithout examiningthe boundary conditions
on p, a, T, and rn The studentwill find it profitable to look for theseanalogies
582
S ystems
-and
also for differences between these two transfer Drocesses-in
remaining chapters ol the text.
the
P robl ems
Ex am ple
18. 6- 1.Blending of M i s c i b l e F l u i d s
E U E S TION S
PR(
l 8.A r
D ehumi di fi c ati on
of A i r
Y
f C hange f or M u f t i c o m p o n e n t
Syste m s
the
Problems
583
use, this situation occurs at Re greater than lOa to 2 x 104. At lower Re the
Reynolds number has a pronounced effect. This behavior has been substantiated
by a number of different investigators.3
ng o f M iscible Fluid s
lnalysis the general form of a correlation
fluids in an agitatedtank. Assume that
ntially the same physical properties.
t the achievementof "equal degreesof
the achievement of the same reduced
)r any component A the concentration
*r 0, " * )
rosition variables,rlD and:/D, respeceller. It will also be convenientto define
V, alND, and plpN2D2, respectively,in
rpeller, revolutions per unit time, and
ieen that .t,q(r*,0, z*) dependsupon /*,
ndary conditions. Here Re : D2Nplp,
lt among the initial conditions are the
ner in which they are introduced to the
nixing.
dimensionlessgroups can be further
imentally observedthat if the tank is
that is, the fluid surface is effectively
absenceof a free fluid surface, gravitarre tnimportant. At a high Rcynolds
also be neglected2
so that :r1(r*, 0, z*)
mixing time is constantfor any desired
number of revolutions of the impellcr
is fixed. For mosl impellersin common
nt for verticalcylindricaltankswith axially
:ed strips,with their flat surfaccsin planes
endingfrorn the top to the bottom of the
he tank center.
noldsnumbers
can bc seenintuitivelyfrom
) becomcs
small in relzrtionto thc accclcrartsare dangcrous,however,and thc effect
neighborhood
of solid surfaces.Herc the
te neighborhood
of solid surfaccsis small
rcussion
of the ellcct of Reynoldsnuntber,
:Graw-Hill,Ncw York (1955),Chaptcr4.
. numberscan bestbe secnfrom thc timeAt high Reynoldsnunrbersthe turbulent
rleculardiffusionexceptin the immediate
QU E S TION S
FOR D IS C U S S ION
1 D i scuss the appl i cabi l i ty of the equati ons of change as devcl oped i n Chapters 3 and
l0 t o the descri pti on of systemsof more than one chemi cal speci es.
2 . A s the concentrati on of component I of a bi nary mi xture becomesvery s mal l , both
p a nd c become nearl y constant; both E qs. l 8.l -17 and l 9 are then val i d. C ompari s on
o f these tw o equati ons suggeststhat u : r'*. Is thi s true ?
3 . When i s (V . r'*) equal to zero?
4 . Is the defi ni ti on of q gi ven i n C hapter 8 sui tabl e to descri becombi ned heat and mas s
tr a nsfer i n systents of i nterdi ffusi ng pai rs of i sotopcs? Gcometri c i som ers ? Opti c al
isomers ?
5 . What does the term X ;F;J1 mean?
6. What are Fick's first and second laws ? Under what circumstances are they applicable ?
7. Show that forccd diffusion does not occur when the same extcrnal force oer unit
m a s s acts on al l speci es.
8 . D efi ne the S oret coe{fi ci ent. What are i ts uni ts?
9 . Why shoul d theconnecti ng tube i n Fi gure 18.5-2 be smal l i n di ametc r? N eed i t be
in sul ated?
10. The ratio of parlial specific volumes of PbNO3 and water is greater than the corresp o ndi ng rati o for egg al bumi n and w atcr. H ow ever, i t i s harder to scparatcthe former by
u ltr acentri fugi ng than the l atter. Why?
1 1. What happens to the w ater i n E xampl e 18.5-4?
1 2. In gaseous di ffusi on systems ai r i s usual l y treated as a si ngl e compo nent. Is thi s
r e a sonabl e?
1 3. A gas i i s di ffusi ng through a mi xture of tw o heavy i sotopesTandT*. W hen c an thi s
system be consi dercdas a bi nary onc')
1 4. C omparc the effects of mass transfer on si mul taneous heat transfer w i th thos e of
h ca t transfer on si mul taneousmass transfcr.
1 5. C ornpare the !]tn and D ,; used i n thi s chapter.
1 6. What are the mass transfer anal ogs of the Grashof and P randtl numb ers ?
1 7. In w hat w ays are hcat and mass transfer anal ogous and i n w hat w ays d o they di ffer?
1 8. Why i s the ri ght si de of E q. 18.5-9 grcater than uni ry?
1 9. H ow do forced and oressuredi ffusi on di ffer'l
P R OB LE MS
l8 .Ar
D ehumi di fi cati on
of A i r
Consi dcr a system such as that pi ctured i n Fi g. 18.5 1 i n w hi ch thc vapor i s H ,O and
th e stagnant gas i s ai r. A ssume the fol l ow i ng condi ti ons (w hi ch are repres c ntati rc i n ai r
co n di ti oni ng): (i ) at : : d, 7 : 80' F, and r",,, : 0.018; (i i ) at z : 0, f : 50' F.
3 E. A . Fox and V . E . C ex, A .l .C h.E . Journal ,2, 539 544 (1956); H . K ramers , G. M.
Ba a rs,andW.H .K nol l ,
C hen.E ns.S ci .,2,35 42(19.55); J.G.vandcV usse, C hc nt.E nq.
Sci.,4, 178 200,209,220 (t955).
58,f
S yrtems
Problems
a. Calculatethe ratio
(r8.A-r)
I - exp (NA,e,alk)6
a.+
dt
+ ( v. p, r ')* ( v .j) : 11
b. -i i + ( v. cr u*)+ ( v. Jr *) : R/
dt
z i s i n centi meten
Rr'
v1
18.J, Mobi l i ty
CrH. * 3H2+cysls-6.H,,
( | 8 . E - t)
l 0-'
l 0-.
l 0-c
l 0-'
l0-o
Answer: Component:
cQi^, g-mole cm-r sec-r x 10..
o :3 .6 1 'l
whereas, for Or,
o :3 .4 3 3
C.Ho
6.63
H2 CoH.
20.8 8.71
CH.
60.
o : 3 .6 8
Ch ange f or Mult i c o m p o n e n t
S yste m r
585
Pr o bl ems
(r8.A-r)
ofyour answer?
the significance
Answer:a. 1.004
{, and D, achievedin the simple thermal
er the followingconditions: fr is 200'K,
thechargeis 0.10,and the effectiveaverag
k. havebeenevaluated?
erl: a. xr, is higherby 0.0183in hot bulb
, . 3 30' K
ofile when a typical albumin solution is
s the force of gravity under the following
OT
( 1 8 .G- l )
+ ( V . p , r ') *( Y . j ) : r t
(18.c-2)
S how that E qs. 18.4-7 through I I may be combi ned to yi el d E q. 18.4-14 for the s pec i al
case of a binary mixture. (It will probably be convenient to take advantage of the relation
,000
ution : MAI VA : 1.34g/cm3
t/ o : 5 x 10-6
rlution: 1.00g/cm3
Answer:rt: 5 x l0-c exp (-22.12);
z is in centimeters
i n * in:O.)
Diffusion
18.1, Pressure
B to obtain
for species
equation
withtheanalogous
Eq. 18.5-17
a. Combine
( 18. r - l)
,rlticomponentGaseousMixture
n e gl i gi bl e. (S ee P robl cm 18.C .)
gas-phasehydrogenationof
bce-catalyzeci
non occurs:
1 8 .J, Mobi l i ty
cyclo-CrH,,
( | 8. E- l)
24.2 x
1 . 9 5x
6.21x
20.7x
41 . 3x
5.45x
I8 .K3
l0-c
10-6
l0-t
l0-'
l 0-'
l0-'
Hr C6Hrt
C.H.
-rsec-rx 10.. 6.63 2 0 . 8 8 . 7 1
rz. Estimate the total force required to move one equivalent of silver ions through a
1solution at I cm sec 1 at 25" C if the diffusivity of silver in the solution is 10-5 cmz sec
b. Comparable forces are clearly required to move uncharged species. What provides
the motive force for such materials in ordinary diffusion?
Answer: a. 2.53 x lOe kilograms force
o : 3 . 6 1 7A"
,
- : 9 7 . 0 'K
o : 3.433
A,
1 : tt:.0" r
o:3.681 A,
- : 9 1 . 5 'K
CH{
60.
a n d, for N r,
K
s86
S ystemr
a. Compute cQABfor the diffusion of methane in air at 300" K, treating air as one
component with the Lennard-Jones parameters given above.
b. Compute cQ A^for methane in air at 300" K, taking air to be 2l rnole per cent oxygen
and 79 mole per cent nitrogen. Assume that the nitrogen and oxygen move at the same
velocity.
Note that the two methods are in good agreement, as is usually to be expected. In cases
in which the relative concentrations or ffuxes of nitrogen and oxygen vary appreciably
they should be treated as separate components.
Problems
['
1 8 . L 3 D i f f u s i v i t y in a n Aq u e o u s So lu tio n o f a Sin gl e S al t
When a single salt (Me\"(Xa)D
diffuses through water in the absence of electric current,
the molar fluxes J.* of the two ionic species are related by the requirement of electrical
neutrality. Show by a procedure analogous to that used in Example 18.5-4 that, in dilute
solution, this requirement may be used to determine the following relation between the
di f f u s i v i t y o f t h e s alt in wa te r , 9 ,*,a n d th e d iffu sivitie sof the ani on and cati on, 9r,and
9r,,, respectively:
On _ ? *.( a * p)
-. (18.L-r)
'"p9r, * agx.
cg m '
,/:J-tnl;
- !,1,:o: ( T o-,;) ( +
\o
Here B :
-(N,a. * Nc,)eo,^''6lk^h an
S h o w h o w t o g e t Eq . 1 8 .1 l9 a fr o m Eq . l8 .l- 1 9 .
Nole: Solution is lengthy.
I8.Ns
T= Tc
C o n d e n s a t io n o f M ixe d Va p o r s2
Chloroform (C) and benzene (B) vapors are condensing on a cold surface from an
eq u i m o l a r m i x t u r e a t I a tm . ( Se e F ig . 1 8 .N.) T h e te m peratureT"of thecol dsurfacecan
be varied. The more volatile species (C) accumulates near the cold surface, so that the
condensation process is retarded by the presenceofa gas "film" in which both the temperature and the composition depend on the distance z from the liquid surface. The film thickness d is 0.1 mm, and the heat-transfer coefficient ft of the condensate film is 200 Btu hr-l
f t - ' ? o F - r . T h e r a t i o o fb e n ze n e to ch lo r o fo r m in th e condensate can be consi dered as
eq u a l t o t h e r a t i o of r a te s o f co n d e n sa tio na n d th e fo llow i ng data may be used:
7rc : 0.050cmz sec r;
Co c:
C on:22.8
0
0
Saturation
temPerature,
"c
0 .1 0 0.20
0 .4 0 t0 .5 0 t0.60
0. 29 10. 36 1 0 . 4 4
1.00
0.54 | 0.66
77. t | 76. 4 | 7 5 . 3 | 1 4 . 0 | 7 t . 9
587
Pr o bl ems
a. Show that the total molar rate of condensation is
-(N^a,
* Na:cff ne=#,\:'ff ne=#\ 08N-,)
0 and d referto conditionsalz:0
andz: d. The quantityz!)isthe
Here the subscripts
mole fraction of component ,{ in the condensate.
g ig
D. Show that the energy flux through the condensate
flm at z :
(--!
-i',,, 1N,,+ N",; (r8.N-2)
l\t-e-01-,\
HereB : -(N.e,* Nc)ee,^r"6lk^,*
andQ,-1. : a']'e,"l rti'e,".
-!,1,:o:(ra-rJ({+)
'-\6
( 18. L- l)
o * a9r.
B oundaryof
stagnantgas film
rB d =rC 6 =0.50
i g. 1
C o n ti nu it y
t - t9.
T=Tc
T :
tre condensing on a cold surface from an
The temperature 7" of the cold surface can
umulatesnear the cold surface, so that the
:eof a gas "film" in which both the temperace z from the liquid surface. The film thickent , of the condensate film is 200 Btu hr-r
rr in the condensate can be considered as
I the following data may be used:
r - m ol e" F ;
e ,n:
2 2 . 8 B t u / l b - m ole " F
T o : 7 6 . 4 'C .
Drrectionof movemenl
of vapor
of mixedvapors.
Fig. 18.N. Condensation
c. Estimatethe ratesof condensationand the compositionof the condensatefor several
condenserwall temperatures. Note that the calculation will be simplified by first choosing
a condensatecomposition. (i) This choice permits direct calculation of Nr, * Ns,
from the result of part (a). (ii) The energy flux through the condensatefilm may then be
calculated from the result of part (D). (iii) The required wall temperature may then be
estimatedby an energy balance through the condensatefilm. In making this energy
film occursby conduction
balance,assumethat all energytransportthroughthe condensate
accordingto the expressionqz : h(7" - T).
Sampleansvr'er:If I" is 86" F, the rate of condensationwill be 1.26lb-moleshr-r ft-2
and the condensatewill be 44 mole per cent chloroform.
d. When, if ever,will the condensatebe in equilibrium with the saturatedvaPor?
e. What is the'(approximate)minimum temPeraturethat can be maintained at the
interfaceand what will the (exact) compositionof the condensatebe
condensate-vapor
under theselimiting conditions? Explain the significanceof your answers.
18.O, Constant-Evaporating Mixtures
A mixture of toluene and ethanol is evaporating through a one-dimensionalstagrant
nitrogen film of thicknessd to a stream of pure nitrogen. The entire systemis maintained
588
S ystems
diffusivities.of.toluene and
at 60" F and at constant pressure. The ratio of the binary
e tha no linn itrog en( 9y t "lgo, u) is about 0' 695, and t h e v a p o r - l i q u i d e q u i l i b r i u m d a t a f o r
systemat 60'F are
the toluene-ethanol
Mole fraction toluene in liquid
0.096
0.14'7
388
Total pressure,mm Hg
0. 15 5
39'7
0.233
o.274
0.375
0.242
0.256
0.277
391
395
P robl ems
=:v
taE
390
9!!x
R
Fb
;Y=
mixture of toluene
It is desired to determine the composition of the constant-evaporating
a n d e t h a n o , l ( i . e . 'th e liq u id co m p o sitio n fo r wh ich th e r ati oofevaporati onratesi sthe
r a t i o o f c o n c e n t r a tio n sin th e liq u id ) u n d e r a va r ie tyo fcondi ti ons.A ssumei deal gas
behavior.
r-;
6)
"Em
6)
x
F
(oo) . t
It
v^
L-
c
08.o-l )
mmHg,760mm
of3e6
tofalpresslure
"t;::l,i::;:XT:i:Ji:1:11,H:':il're *rg
--
i liiliillli:[:::::;il.^;l.,,,.
{_
!q
:O
-l
l8.Ps
Di ffus i on of A through a S tr
ComP os i ti on
4F
/t_( t - 'uJ
- \e xP
-
(0 -
c. We maywritcrr' :
'^o)
exP
rr
)or"Otl .
to c
and integrate
into this expression
r/
?tnt?^c
H ere r:
contai ne d i n rrr.
' o : l l -fl l g
r \e x
and Q:11
-t
590
S ystems
P robl ems
s' - ( Ar '
-l
dr
rI
-
r^(cr*t
d-L
* (BPeo - A4t,
+ (BPCa_ CPA
xP
Catalyticsurface
a t wh ich
p P + qQ
A- - >
z =6
( l 8.s-l)
(r 8.s-2)
Here vro: Nilcgpe, Ap: Q - p)rr - 1, Bp: (l - rp)P,Cr: prr' The quantities
Aa, Bc, and Ce may be obtained by everywherereplacingP by Q and p by q. In these
rp:9rrf 9^" and ro: 9ral9tl.
expressions
6. Take the LaplacetransformofEqs. 18.S-l and 2 with resPectto r"o( to obtain the
for the transformedmole fractions;"(s) and fq(s):
foltowing algebraicexpressions
r r o* Cps - r + Bp e
s- Ap
Z^:
'
reo *
-
Cos-'t * Boip
s- Ao
(l 8.s-3)
(r8.s-4)
Y
,f Change for Multicomponent Systems
Problems
591
c. Solvetheseequationssimultaneouslyto get
rp.'sz* (Brrqo - Aerro * Cr)s * (BpCr)- CpAd I
_
'P -s, - (Ap + Aals + UpAa - BpU
;
ngeof kineticenergyper unit massin multitakingthe dot productof u and the equation
(l 8.s-5)
ckingvvithA+ PP+ qQ
re positivez-directionthrough a flat gas film
d there is a solid catalytic surfaceat which z{
lI
-l
d+ -
r"o(ured+urQl
d.-eo-'PQl)
d- L
+ (Bprao- A{^
Cp)(eq+'pe1
--ea-'pel)
_,,leq-,ecl
* (BpCc- C.lo)\
- |
,,
- ""-,.0{
,_
- l\l
(18.s-6)
) )
I
dic surface
I w h ich
A -pP l qQ.
The reaction rate may be
p : ,ro nnd no: rgoi both of these mole
P and Q are
i for components
' IB p c *C r
* Bq p * Cq
(1 8 .s -1 )
(l 8.s-2)
B*q
.-es-L+ BaiP
-A^
(18.S-3)
(18.S-4)