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A Theoretical Study of Isotope Separation by Displacement Chromatography

Article  in  Separation Science and Technology · January 1985

DOI: 10.1080/01496398508060688

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Yasuhiko Fujii Takao Oi

Atox Co. Ltd Sophia University
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SEPARATJ
ONSCI
ENCEANDTECHNOLOGY,201
5A6)
,pp.377-
392.1
985

ATheoret
icaISt
udyoHsotopeSepar
ati
onby
Di
spl
acenentCJlrOmat
Ogr
aPll
y

Y FUJ
lt
書M.AI
, DA,and M OKAM OTO
RESEARCHL J
u30RATORYFORNUCLEARREACTORS
TOKYOI NS
TITUTEOFTECHNOLOGY
0-OKAYAMA.MEGUROKU､TOKYO152

T 01
DEPARTMENTOFCJ IEMIS
TRY
SOPHrAUNIVEft
SrT
Y
KIOT
ICHO.CHIYODAKU.TOKYO1
02

Abt
rJCt

As etorequa(1
0nSISdenved一〇des
cnbemathematIcall
ytheI
sot
opedlSt
rlbu(
101
1
mt heseparat
10np r
O0S SOfdlS
pJa
cemer[
tcl
lrOmatOgraphyETnPhasIS)
iplaced
or
LnOnS t
eady-st
atel
SOtOPCaCC
umulatl
OnlnrhcboundaryT eg
lOr
10faml gral
IOn
band Ther e
sult
slndlCat
ethatthe)sot
opcprofT
Ll
el n( hem l
gra
t10nband lS
ex
pr e
ssedby

R - ド (I-Ro
)/日+(eE
kRD
L- 1
)ek
(xーL
)1

whereA E ,A.Roュ, and二rareL oca)Isot

oper raC
110n, SCPara
tLOZ]COef
rl
Clent
,SI
opc
coer
rICer
] l
t,Ongll
la llS
OtOPefrac t0n.ml
1 grat
10nleng th.andpos l
tl
OnLntheband,
res
pectl
VCly M at
hcm at l
Caltreatme ntlSeJL
tendedt ot hedetem lnatl
OnOrHETP
orexpenme ntalsyslemSThE :re htl
Onb e t
weenther TOntalIs
ot operal
10rLandthe
nl
T grat
lOnlengthl SalsoobtalnedTh ey aL
ldl
【yOft hedc nvede quat1
0nSISVenf
ied
byus l
ngt her epoTtede xpenme nt
alda taonb oronl s
otopes epara
tLOnbyLOn-
cxchangechr oT
natOg T
aPhy

`
Towhom c
oTT
eSpOnde
nces
houl
dbea
ddr
ess
ed

317

Co
pynght
①198
5byMa
rce
lDe
kke
r,T
nc 01
49i3
95/
85/
2005･
0377S350/
0
 L
NTF
tODUCT1
0N

Isotopes eparatlOn byi on-exchangechr omat ogr aphyhasbe ene x-

tensivelystudl e
dwhi leseekLngI tspr aCtlCalapp】 1
Cat l
Ont Ot hepr oduc t
lOn
ore nrichedi sotop
eS ･Ther emar kabl es uc cessln1 5Ni sotopeennchr nent
byl hlSme thodwasde s
cnbe dbySpe ddi ng( I)Re gaT dlngt heme chani sm
ortheennchmenLpr∝ e s
s,Gl ueck aurde v
elopedat heoTTf l
OrChr omat O-
graphl CI s
ot ope S eparation bas ed on t wo･ pha s ee qul ll
bdum ( 2.3) ･
Kaki hanadenv ede quat i
onsf ori sotope s epar at10n bydi splacement
chromat ogT aPhybas edon( hec onc eptorl ndi vlduaLI SOtOPICmassf lows
inag eneralizedhomoge neousme dlum ( 4,5)Anumehc alme (hodwas
reportedbyFu J
ine( 6)andCal us aru( 8),andanal ytICalwor kwasdoneby
Jacque sondi splaceme ntennchme nt( 7)
Mos tort heabov e-ment 】onedwor khasbe ens uccessrullyappl l
e dt o
low-enr i
chmenti sotop
e s e
par atlOn S yS(ems ,howe ve rt herehasbe en
ambi gultyandI nconve nienc etnt heappl i
cat l
OnOrL het he orleStOhl ghl y
ennche ds ystems Theonl yempl nC alc quat 10n f orhi ghlye nnc he d
syst
e mswasobl alne d byGl ue ckaur( 3)and appl l
c dt o■ 5Ni sotope
separat I
onr epo.ledbySpe dding･Ther ear es pe clrl
Cdl rrlCult)
esl nt he
generalt r
ea( mentort henons teady- st
atei s
otopes epar atl
OnPr oce ssWhen
ltlSC Ontinuous lyde vel
opl ng f rom l ow de gree st o high de greesof
enrlChment .l nt he pr esentpa e rt
p he a uthor sdenv ea c onve ni ent
equat i
onappl lcablelot henons teady- slateenr ichmentpr oc esscov ennga
wldcr ang eofennchmcnLde g
r ees.Thee quat ionsder iveda- eus efulT n
esti
mal l
ng t he reaslbllit
y ort heennchments ys temsexp e nme ntal l
y
cons i
der e
d

THEOF
tY

Displac emcntchr omat ographyl Sanef ficientpr ∝e ssForobt ainlng

enr jc
Tledi sotopes Thi soper atlOn i schar acte r
ized by s har p band
boundane sa tt heml graLt
onbande ndsT nt hepr esentwor kwemal nly
de alwl thdl Splac ementoper atlng] nabr eakt hroughmannerwher et he
shar pboundar yl Satt hef ronte nd･
Tnac hTOTTlaLog raphi cs epar aljon s yst
em,onei sotopeS pe cies,e･g･
,
isotopeA. mov esf orwar dfastert handoe stheot he risotope･Tof ormul ate
thes e parationPr oc es s
,t r
eatTnentuS uaHyc ommenc eswit hs e
ttlnguPa
rundame nl atdl rruSione quat]Onf oroneort hes pe ci
e sandt hens olvIT
lg
(hee quat 10n undert he appr opnat econdl 【
10nS ,Thl Smat hemat i
cal
treatme nti sper LInentWhe nl SOt OPe SA andBbe hav easI nde pendent
spe ci
e sl nt hec as eord】 splaceme ntchromal ography ,speciesAandB
interferewi the ac hot her.ani nc re aseinthec onc entr
at l
OnOr九I Salway s
l
SOTOPESEF
'ARATI
ON BY Dt
SPLACEMENTCHROMATOGRAPHY l
37

coupledwi t
hade creasei nthec oncent
ratl
OnOH l ,sincethetotal
concentr
aLI
On15S t
rict一
yfixedint heml gr
ati
onban d.Toe xpr
essSucha
coupledT
nOVeme ntltisrele
vantt
oc o-1S
ldertherel
atl
vemo vemell
tOrthe
speci
esinvol
vedr at
he rthantheI ndependentmov ementorthespeci
e s
Thisconslder
atl
onc or r
esporL
dstoc hemlCaltrea
tme n
tlnWhi cho】一
eO f
thelS
OtOPeS15Chosena stheretT
erenccma t
ena l
,1T
tCOrL
tT
aSttOtheusual
patt
et
llOruSlngtheT nediumast her eE
T
ere
nce -

FL
Jr
ldaner
l
talEqL
Jat
ior
l

p
nlCt
ota一
conc
ent
rat
ionorl
SOt
OPe
Sinamlg
ra1
10nbandi
sac
ons
tant
,
CD,

C^十C8-Co (
0 <
.
r くL) (l
)
CA-Co
凡 CB-C｡
(I1月)

wher
es ubsc
dptsAand8denote(
heisot
opes,
andAi si
sot
opefract
ionof
AhEqua t
ion(1)isus
edtl
Orbreakt
hrougT
lmi g
rat
lOn.Th15Iela
tLOnis
aT
)Pl
lCabL
eWt hi
nthel
imlt
edwldthorth
eba71
dinthecaseorfi
xedband
ig
m r
ationUs i
ngthet
ermsinEq･(1)
,tt
lCi
sot
operati
oisdert
neda s

r =CA/CB=I
U(I-R) (
2)

Thei s
otopee nnChme T
ltProc essln【hemigrati
onbandi sinlerpret
cdi n
suchawa yt hat(a)thee nnc hme ntnowong■ nate
sf rom thei nhere ヮt
l
s ot
opee t
rcctlnVO】Yedi nt hes ystemlO,)partort hee nri
chme ntnow. tS
cancel
e d by a dl f
rusion l low i nduced byt heg r
adi e
ntor) sotopt c
concentra
tion,(C)thee nnc hmen(nowI SPartl
yc onsume dL T
IInCrCaSlng
thecotl
Cent T
atl
OnOrt heis otopeorc ot
lC
em( name 一ythehol dup),and( d)
therestofthee nnchme ntnowf orwardthrought heTTugrali
onbanda sa
poteT
lt
latPr o
duc tnow.
Toc onsidere a
chmi croscopicn owc ompon ent,Wes e
tupe quatlOnS
basedont her e
lati
venowdi ffer
e ncebetweenisotopesAa nd8. Thenu又
oreactlis
o t
opicnowI Se xpre s
sedby

OA-CAV.. ￠E
I=CBVB 3
()

wher
eVAandVBaretheove
ral
lmigrat
ionyel
oci
ti
esoris
otopesAandB
Bas
edontheconc
ept
or i
so【
Opecf
rec
t11
1theproc
ess
,theennchmcntf
low
I
S≠Tlt
tenaS
 FUJl
lETAL_

A(
PE -CA(V^- VB
) (
4)

Si
ncet
hei
sot
op
e ef
YT
ec
tint
hes
yst
em l
Sdef
ine
das

e-(VA- VB
)/VB

t
heennc
hmentnow i
sex
pre
ssedas

AOE= eCAVB (
5)

whe
ree)sthese
parati
oncoemc
lentOrt
hesys
tem.
Therel
ati
vedir
rusl
Onf一
owISuSuaHygl
Veninthetom

A￠D= -(
DAdCA
/dx-DB
｡CB
/dx)

whereDA andDBar e( hes e

lf-
difr
uslOnCOerf
icientsorthegl Veni sotopes.
ThisequatlOnl SaPPJIC abl
ewhene achnowmov esI
nde pende ntly.Inthe
casewhe ret het otalc oncentra(i
on isconstant,thedl frerencei nthe
dir
rus10nmowsOrl SOtOPe S】nducesacompens at l
ngnowt hatc anc elst
he
L
mbal ancelnt hedl rr
uS 10nnow Toav oldthl
SC OmP】exlty,WeObt aineda
mores tri
ctl
yappl i
cabl eequationt oexpr
esst her e
lati
v edl 肌l S
IOnnow
(Apperldi
xI )

A￠D= -DCB
d(CA
/CB
)/a.
r (
6)

Therda
tlVehol
dupf
lowusedt
ochanget
heI
sot
opeC
OnC
ent
rat
lOnL
nthe
naT
TOWregi
onAJatposi
ti
onIisglV
enby

AIA= -Ax(
dCA
/d1-dCB
/dt)--2AxdC.
/dt

Thusweobt
aint
hepr
oduc
tionnowas

A中′= AOE+A￠D+A oA
=E
CAV8-DCB
d(CA
/C｡
)/dx-2AxdC^
/dt (
7)

Tosimp)i
fyt
hemathemat
lCalex
p-e
ssion,Weint
roduc
eadi mens
ionl
ess
equat
lOnObt
alne
dbydivl
dlngEq (7
)byt henuxorlS OPeB,￠C
Ot ,

Jp= A中,
/中,
, ,
JE= AやE/OB JD= AOD/
中L' J.= A中々
/￠B
l
SOTOPESEPARAT1
0N BYDI
SPLACEMENTCHROMATOGRAPHY 381

Jp=JE+JD+J ん
=e
r-Ddr
/dx-2(
Ax/
C,VB
)dCA
/dT (
8)

Equa tl
On( 8)1 Sthefundament alequat ion.To applyl ttOthea ct
ual
separatl
ons ystems,Wec onslderthreetypl C
alc ase
sort heoperati
onal
St
ate.
1St eadySt at
e.lnthlSStatethese paratl
Onpr ocessProce
edswl t
hout
concentrat
lOn Change sint he sys
tem Mor eover,no productl
On lS
obtai
neds incet heproducti
onnow i stotall
yc ancele
dbyma cros
copIC
dlfr
us10n betwe entheenr iched partand t hede plet
ed partlnt he
separatl
OnS y
stem Ther e
fl
Ore,thisst
ateisex pressedbyJp =JA=0Thi s
le
adst o

JE+JD=0 (
9)

2 Qua Sl
-Ste
adyState/Dynami cSteadySt at
eThedynami cst
eadystat e
corr
espondst othenomaImodeorope r
at 1
0nOrC heml Cals
epara
ti on
pl
ants The pl ants are op
er ated undert he c ondlt
ion orc onstant
pT
Dduc l
ivlt
yandnoho一 dupchange;t hatl S
,Jp Ic onstantandJh=0
Whe nthlSmathematicalmode lisappliedtoaml CrOSC
Opl COrmOme nt al
ma s
sbal ancelnaki neticprocess,t
hl SStateuSua uyref er
stOaquaS l-
st
eadystate.Thei.
undame ntaLequaE1
0nf ort hequas l-
St
e adyst
ateort he
dynarnl
CS te
adystat
el SaCCOrdlngl
ygl Venby

JE +JD = C
OnS
tant ([
0)

3.NonsteadySt
ate.T
ng ener
al,nonst
eady-
stat
edi
spla
cementenri
ch-
me ntref
erstotheseparat
lOnProcessOPer
atedunderthet
otalref
lux
cond]t
ionwi thnoproducton;name
i l
y,JpI0 Weobt aint
heg erL
eral
r
e l
ati
onfl
opt hi
sst
ateas

JE+JD+JA-0 (
ll)

Equa ti
on( 1L)1
SaPartialdiL
Tere
ntialequat1
0nI (lSext
remelydif
ficultto
solvethee quati
onfわrg ener
alc ondltl
OnSOnl yl nllmlt
edc as
esor ,for
examp le,tow degre
e sOre nnC hme ntI SEq ( ll)solve
d wl t
hs ome
approx l
mat i
ons･lnsuchc as
e s
,Eq. (11)lSexpressedlntermsOri s
ot ope
仔a ct
ionR,andbe come sort hes amet ypea st heequati
onpr evi
ous ly
studl
e d(3.4).
 FUJl
lETAL_

l
さOt
OPi
cConcent
rさt
ionFuncti
ons

Steady
-Stateis
otop
e ennchmentlSatt
ame dbylongdi st
anceTTHgT
ati
on
wt
i hanaT TOW band.Themat hemati
caltre
atmentsfl
Ort hisst
atehave
beenwel lstudie
d( I,gll2) L
nthepr e
sentPap
erabr ierdescnpti
onlS
ma deorthisprocesstocompareitw
ithr"ns t
eadyst
atee nTi
chmenLThe
rundamcntale quatt
onforthisst
atelSgiv
enbyEq･( 9),whichiswnt t
en
aS

s
r-(
D/V)
dr/
dxI0 (
9')

By.
nte
gral
ingEq(
9')undert
hec
ond.
一onTI'
i oal
x=xo
･wuhL
het
err
ns
,D,andVc
e ons
tant
,weobt
aint
hei
sot
opl
CCOnC
ent
rat
lOnf
unc
tlOnf
or
s
teady-
sta
tee
nnchmentas

rIr
.ck
s(
]Jo
l A.I eV/
D (1
2)

wher ek ∫ref
Terst othes lopec oerfic】entoft l
leS teadyS tate,roist heongl nal
l
S OtOPCr atio,andx｡i sthepos itl
Onl nt hebandwhe ret hei sotoper atlO
i
se o
qualt r o
.
The nons te ady･sLate enrichn le ntPr oc ess,On t he ot herhand,1 S
de scnbe dl nPdnci plebyEq ( ll )Duet ot hepr c yious tyme nt10rLed
di r
tT
tcul ti
esl nObt ainingag erLera)s ol ut10nOf L Eq.(L I),Wepr opos et he
conc eptors t
e pwi s
eenr ichTTt
entl nml gratlOnTheT T)
tgrationbandmov es
loTWar d,bui l
di ngane wf rontalmi cros cgmentDunngt hes hor tpenodof
thes t
e pwi seror Tnationofane ws egTTl
ent ,thel SOtOPICC OnC entrati
oni n
themlgr ationbar Ldi sas sume dl or e mai ni ntactaTl dt hepr oduc=l ow
dlSChar gedF r
omt hef r
ontbandde pos it
si nt hene ws egment . ThlSpro cess
isr egar dedast hemome ntalorquas l-
S t
e adys tate,whichs ug geststhatEq･
(10)l SaPPl lCablet ol hlSSySleT
Tll nPl aceorEq ( ll)Ont hebas i
sort he
abov e as sumpt 10n,We Obt alnt he e quat 10n f ort he nons teady-s t
ate
enti ehme ntbys olvlngEq. (10)unde rthec otl
dl l
10nSr=, oandd r/
血 -0
at x=0,wi the,D,andVc ons lant :

Er -(
D/V)
dr/
dx-c
r. (
13)

Futl
hcr
TnOr
e,iti
sofirt
ter
estt
oexaminethest
ateorthee
xtre
mefront
se
gmentwheretheproductnow de
post
tsareC
OnVert
edtotheho)
dup
now Thiss
tat
eisex
press
edby

JpZJ A (
14)
I
SOTOPESEP
ARATf
ONBYDI
SPLACEMENTCHROMATOGRAPHY 3
43

Combl
nat
ionorEqs(
8)and(
14)l
eadst
o

JE+JD -0
Thisequati
on)∼thesameasonepr evi
ouslyobtainedfort
hesteadyst
ate
,
Eq (9)Thi sme ansthatthesteady-S
tat
emode lisappl
lCabletothe
ext
remefT
rontsegmentlnthenonsteadystate.
Usi
ngt hesamecondlt
ionsasforEq ( 3
1 ,andpayl
) ngat
(entl
OntOthe
re
glOn nearthef r
ontband endwhos epos it
LOn islndl
Cated bythe
mlgra
tior
llengt
hI .
,Weobtalnt
hel SOt
OplCC OnCentr
atl
Onfl
unCtl
OnaS

r- r｡ -gel
(xL
) (1
3')
k-e
V/D. g-r
L-r
D
whe r
ek l St hes l
ope C oerficl
entOrt hef unc ti
on l ornons t
eady- s一ate
endchme ntandr Listhei 50tOper a110atthefronte nd. TtShouldbenot e d
thatthev al
ueorex p( -kL) ,
obt a)nedbys ubst)tut
lngX -Ol nEq ( 13'),LS
approx lmatedt obez er
o,S lnCeI s
otopee nrichme nti sobs ervedaf ter
sufT
Iclenll
yl ongml gratl
OnSEquat On(
l 3'
1 )cl
e arl
yl ndlC at
eSthalp] ott
lng
ol1n(r-r o
)a galnSt(xIL ･)rorFx Perlmentaldatayl el
dsal l
nearlinewt h
as opeorkdes
l pltetheml gT at
lOnl engthort hee xtentore nrichme nt
TovI S
ualizet hepr ofT
ll
eofi sotop
e a ccumul ationalt hef rontband
re On,itlS neCeS
gL SatYt Oexpr esst hetem gbyot herop er atl
Onalf ac t
or s
.
Forthi sPurposeEq( 13')i
sr earrange dusingtheter mt orisot
opef rac t
ion
Ai npl aceori sotop
er t
l
O
ar
R IR｡≡(IlR｡
)2
ge`
(xーL
) (1+(I- R｡
/l )gek
(LIL
)l (1
5)

Aspre
sent
edl
nApp
e ndl
XTl
,theI
nte
gralorEq,
(15
)be
t enx= 0andL
we
l
eadslo

g- (
ech
RoL- I
)/(11R｡
) (1
6)

Hence
,weobt
alnt
hei
sot
op
e pr
ori
lef
or(
hee
nnc
hmentatt
henons
teady-
s
tat
eas

R - 1-(I-R｡
)H+(eEARoL- 1)ek(
/ x-L
), (17)

Equat
10n(17)ispar
toranS-shapedFunc
tionl
ntheTa-
1geRo<R<Ia
complet
eSIShap
e isobtai
nedwhe ni-の.Thl Sfunc
tlOnhasas
ym-
metr
iccent
eratthedenect
ionpolntR= (1+Ro)2
/
 FUJl
lETAL

lnt
hee a
rlys
tag
eorenrichment
,whereA de
ia
v t
ess
ll
ght
lyf
rom R
c
(
name
ly,
ekRoL≪ ])
,Eq.
(17)lSS
impli
f
iedto

R = R｡十e
kLR｡
(1-R｡
)e'
Lx-い (1
8)

Equati
on(lS
)1Sex
actlythesameast
heonepre
v l
OuSI
yde
riv
edf l
Oralow
enr
ichments
yst
em( 3
7),base
donthethe
oTYpr
esent
edbyKakihanaetaI
.
4)
(

HETP

Thehei
h te
g qulV
alentt
ot hethe
ore
(ic
alphte
,HETP,olc
hromat
o･
g
raphi
cse
paral
10nSys
tems)Sdenot
edbyH anddef
ine
das

Hdr
/dJ
r-e
r (1
9)

Equat
ion(1
9)l
Sre
arl
'
ang
edt
o

dl
nr/
dx= C
/fl (
19'
)

TheHETPde ET
l
nedbyEq (1 9)i
sanIndicat
oroftheste
epne
ssorthe
is
otopl
CCOnCent
ratl
Onlunctl
OnaSex
press
edintermsorlnr
Atthe.s
tea
dy-st
ateeT
l-
jchment
,HETPI Seasi
lyrela
ted【othes
lop
e
coemcLe
nLThec omblna(
ionorEqs(t2)and(19
)leadsto

H = D/V-e
/A, (
20)

Thev alueorHETPort heslopeofl nri sconstantov

e rtheen【
lrere
glOn
oftheml grat
ionband.
]nthec aseornons t
eady-s
tatee nnchme nLt hesl
op
e 0日nrhcr eas
cs
withani ncreaseorxandT eache sama xlmum V al
uea ttheban dfr
ont
x=L･TheT naXimum s t
opca tt heba ndf r
onti ssec
p i
nct otheglVen
separ
at10nS y
stemandi sexpectedt obek eptconst
antthroughtheentIr
e
processfrom lowe nnchmentt ohi ghe n.
ichme ntunder(henons t
eady
st
ate.A
s me nt10ne
di nt hepr ecedings e
c t
ion,thes t
eady･
stat
emo de l
JE+J D-0 hol dsint hee x
tremer r
on【s e
g mentort henons t
eady-
st
ate
enhchme ntsystem.Thusweobt ain

dl
L nr
/dxL_▲≡￡
/H IA
, (
21)
I
SOTOPESEPARAT1
0N BYDI
SPLACEMENTCHROMATOGRAPHY 3
85

FT
Om Eq (li′
),r
dlnr/
刺, .i=k(L-r
r D
)/TL
,andbythec
ombl
nat
】OnOr
t
hisr
elat
ionandEq (
21),t
hesl
opecoer
rLCl
enti
sgt
venas

k=er
L/H(
rL- ro
)= k,
′L/
(rL
: T
｡) (
22)

Subs
tL
tUt
LOnOrEq (1
6)I
ntoEq.(
22)l
eadst
o

H =er
L/k(
rL- r
.)-壬
1十R｡/(eE
川oL - 1
)le/
k (
23)

WTl
ent heennc
hmentde
gre
elSl
ow (
name
l kRD
y,e L≪ I
),Eq (
23)i
s
s
impli
fi
e dt
o

H =(
e/A)+(L/k2
L,) (
24)

1nt
hecas
eofahLghlyennchedsys
tem,thecurv
eorlnrlnthenonst
eady
s
tat
eapproa
chestheasymptoteorthellnefl
OrtheSt
eady-
Stat
eenhch一
mentThi
sfactl
Se Xpl
alne
dbyt herel
ati
on

dl
nrdx = k(
/ r-r
.)r= kS
/ (,-T
.)r
L/(
TrL- r
.) (
25)

Wlt
hlnt
her
eg1
0nWher
erL>r≫ r
o,t
hes
lopeorb rc
anbeappr
oxl
mat
ed
byk.

Es
tlma
tlonofF
tqL
JiedW gr
r ati
orILengt
handEnr
ichmentV
ndt
h

lT
oexaminethefl
eaSibl
li
y orac
t e
rtall
lChromat
ogr
aphlCennChment
sys
tem,onehast oknow t hemlgr
ati
onl engthr
equlr
edtoobtalnthe
desi
red de
gree orert
nchme nt
.The r el
ati
on be
tweenthe maximum
ennchmentdegreeatthebandfT'
Ontandt hemlgr
atl
Onlengt
hisglven
fr
om Eq (17)by

)
RL- ) -(1-Ro/eM o
L

Or

)1
ekR｡
L = (1/ r
Lf(1- R｡
)/(I- RL
)) (
26)

ThelT
ugratl
OnleT
tgthlSal
soexpr
ess
edbyusi
ngHETPI ns
teadort
he
sl
op
ec oefr
iCi
entA Thecombl
nati
onorEqs(
22)and(
26)l
eadsto
34
8 FUJl
lETAL

I-Ro
L= 2
C (
3
o
;'L _
-RR
o; nT二百 一
RLl
'
聖地
C
2,r
o L

I岩
n (
,,,

Thepl
antequl
l1
br l
um t
】met(t
hetimer
eql
ll
redt
ore
acht
hepr
oduc
tlOn
st
ager
TOT
TIS
lal
llup)lSS
impl
yglVe
nby

T= L/V (
28)

l
nt hepr es
eTltderlVallOnWeaS SuTnet hatisotopI CCOmP OSlt
lOntakesit
s
ong lnalvalueatt hes tartngp
i OIntX =0 ,anddi rrersfrom theong l
nalm
allotherpl acesint heml gTat
lOnband Formos tort heml gr
ati
onband,
howe v e
r,IsotopeC OmPOS it
ionpr actl
Callyapp e arsasapl ateauwl t
han
Isotoper atl
OOrappr OXl matelyr｡.Trwedef inet hee nnc hedpaltast he
areawher ethelSOtOp
er at
ioIShighert hant heong] nalvaluebyatleasta
f
Tactorofi ,thent hewi dthort heenhche dpal tf orthenons te
ady -
stat
e
system,W,1 SObt alne dbys ubstlt
utlngt her elationsI-L= -W and
r=(1+E) loinEq ( 13')andus ingEqs( 16),(
22 ),and( 26)

W = H(
T ｡
L-T)e
(rL)ll
n(r
L-T
｡)/
(er
o) (
29)

APPuCAT1
0N

h or dert oe xami netheyal idit

yort hee quationdenv e
di nt hepr esent
wor k,thee xpenment aldatare portedwer eanal yzedbyus lngt hede r
ived
equatlOnS
Sakumae tals tudiedtheenr i
chme ntorl O
BI sotopebyani on- exchange
chromat ographyc ame doutl nar e versebr eakthroug
h oper ati
on( 14).ln
thiswor k, natur alboTOnl nther or7TIOrboncac idwasr e
dI ntoS eparation
co一umnspac kedwl t
hwe akl
ybas ICani on-e xchanger esi
n,andt hent he
adsorbe dbor onwase l
utedbydi splacementbypur ewat e
r.f oml lnga
shaft)boundar yatt heTe arend Byr ecycl
icus eorpacke dc oluml l
S( )m
long)c onne c tedl nSeries,Chroma tographi cml gratl
OnSWer ep
er forme d
up t o2 5 6m Af t
erml grat
ion t heemuent swer esub je
ctedt o mas s
･
srN
eCtrOme( ry anal ysI
S,and t he i sotop
e r at l
OS Or lob and "B wer e
determi ned.
Toappl yt hee quat 1
0mSder i
v edi nt hepr es
entpaper , t
heIsotopePr Orll
e
Lntheer nue nlwasc onvertedtot hei sotop
e pr oril
eint heml gralionband
inthec olumnatmi gTat1
0nl engthi Fi gure1s howspl otsort hei sotope
ratol
i n( r-r D)agai t
lSlt
hedl StatC
l e(x-I .)lnt he10n･eXChang ec olumn.
l
SOTOPESEP
ARATI
1
[
[ ONBYDI
DUI SPL
ACEMENTCHROMATOGRAPHY
Buo(︻e H]/[gOl
1･1([
gL
gOL])t
] ])- 387

ー
150 -
100 -5
0
DI
StCL
nCe (
XIL)lcm
FJG IThereLa
tl
Onb et
weeT
tth
el S
O(Opeenll
C hme n
(degre
el n(r-ro)andthed】S
tanc
e
f
TDm (h
eb andend(x- I)S
. y
sle
Tn BoTO
nI s otop
eS eP
arat
10nb ydl
SPlae
emerL
tan10T
t-
cxc
hangec
hror
nalo
g r
aphy(
expe
nme r
Lta
ldJ
ataar erT
OmRefl4 )M lg
rat
l
Onl e
ngt
hI -256m
aSlndl
cat
cdforea
chrunOdg lna ll
SO(
OPCrat
LOr0-024 7
5

TheHnear it
yoft heplot
sf oreachr uni ndicatesbot ht hevalldlt
yOfEq
(13')andt hec onstancyofthes 一opec oefrl
Clentkovert heentlreenhched
zone r eg
lOn T twasal sof l
Ound t hatt heval ueork dependson t he
mi grat
ionl eng t
h.Byus I
TlgEq ( 23),theval uesofHETP t l
Ordl ff
l
erent
ml grat
tOnI engthswer ec alcul
ated Theyar epr esentedl n FIg 2al ong
wltht heval uesofk det erT
mnedbyus l
ngt hepl otsl n FIB 1 Fl gure2
clearlyshowst hattheHETP ordl Ererentmlgr atl
Onl engthsI SCOnStant
ove rawi der angeofml grationl engths( f
rom 2t o1 28m)De iat
v ionsl n
flETPval ueswer efわundl ntll
eeXt TeTT
LeCases,1e,mi gr at
ionl engthsoilI
 t
Iu
J3/
1 Iu∼歪 も 0∪巴 〇]

■
. ○ O
0_
S

E
)I D □ o

o
1
○
5
⊂
I
1
0
0 □
O □100D
5
0
8
5
O
00
0
.

Ml
grOt
10n l
engt
h LIr
T
I
FIG2HE TPI
sands
lop
ecoefL
iC
lentS(A
)ofthebor
onlSOtO
peS ep
ara t
1
0nb yd I
Spla
ceme nl
On-
anl exch
ang
echro
rna
tog
raphy( □)Ad et
er
lnlne
dbyt heplott
ln
Bl nFLgl( ○)HETP
cal
c u
lat
edbyHETP=cr I
Jk(r/r O),e=DOl,ro=02475,,
/_≡ cxp
c nmentalLS
OtOPC T71t10
a
tbandcn
d.f
romRerJ4Th ed ashe
dllnelSt
hedyera
:
geo rtheHE Tp-
S .
01 8cm

and256m l nt hecas eorIm ml gTatJOn, Chr omaL ogr apT

l yWasC aT
Tie dout
by us mg a s lnBtec o一umn onLy w it houtany c onne ct
mg c ol umns･
Pre sumab) y,thlS ISthepnmer e asonf l
Ort hes mal tHETPval ueOnt he
otherhand,i nt hec aseor256m T TlgT
l 71t10n,t herewasani Tl
leml pt )Onin
theoper ationduet ome chanicaltl'
Oubt cl nt heappar atus( 5
7 )IThi sma y
bet her eas onr OTt het aTgeHETPv alueat256m Thl SplOCe SSOlanl On-
exc hangechr omal ographyhast headv antageoroper ationals t
abl lit
y†oT
me c hanic altroubl esWhent roubleha ppens ,thes upp一yor eluentandt he
clr
C ulati
onort he rT
Tt
OS latedwat erar es toppe dI mme di at
ely.The nt he
columnt emper at urede creases,whichc aus e sads orptl
OnOrt hee xc l
lange
TtSinf T
oT
･ thebor ollionsi nt hesolut i
onphas e.Thus ,isotopel emi llnglS
lowe red.W九ept het roubl eisellmi nate d,t het emp eratureise le
va tedto
the op er ationall eyeland not lT
La)c ondl t
lOnSar er eeS
tabl is
he dl br
chr omat ogr aphi cml grat 1
0n.
Byus ingt hes aTnee XPe dment als t
udyf orbor oni sot
opeS epar ation,the
yalidLtyOfEqs ( 26)a nd (29)wase xami ne d.Flgu re3de pi cts( a)the
Telation be tween maxi mum ennchmentatt he band e nd and t he
l
SOT
OPESEP
ARA
TIONBYDI
SPL
ACE
MENTCHROMATOGRAPHY 9
31
s
a
lt
)ld 一DUl
0
むL
J7-
0
しむqu
JnN l
a)0

ー01 1 0
1 1
00
IsotopcLrqt 1
0rL(l
o母l-B)Qtbondend
'
FI
G.3M' gra
t10
nlel
lg
than dennch'
T.
ent､
Ⅵdlhlnthemn.h
ero†thc
o r
et
lC
alpta
leSVS
L
SO
tO r
a0
Pe t1 att
heban
de r
dS
l ol
l
dcu Ⅳcsa
reCal
cul
at
edf
orth
ebo'onI
soto
peSCPa
rat
lO
n
s
ys
temwlthe=Oof,r
0-02 475ExpenTT
t
CnL
ald
atac.
【e
dfr
omRclJ4(◇)M l
gT
atl
Onle
ngt
h
L
JHE ○)c
TP.( nnc
hmenr∼.dthW/HETP Wswe ,edet
e.
mln亡
db yLhcplo
tsL
nF.gI
HE TP'
susedar
eshowHnF I
昔2

mlgratIOnl engt hexpr essedint er

msoft hes tagenumbe r( L･
/H) .and(b)
t
he r elation be tween t he wldth oft he e nnche d parti n W/ fTand
max l
mume nrlchme Tl
tatt hebande ndThec uIyeswe r
edr awT lbyuslng
t
hes pe cirl
CVal uesof Llheexp
enme nt
alsys tem､e=0 01andR.-01
. 9
8 4
Thepl ot sinFi g.3ar ee xp
enme ntall
yobs ervedval ue
s.ttisse enthatthe
I
:xpenment alval uesar eing oodagr eeT
Tl
e nlwI t
ht hecalculat
e doT l
eS
lnt hepr es
e ntaTlalysISprocedureForc hromatographlC Is
ot opeSepa-
rat
ion,i fRo H,andRL ar
, egLVen,therequi re
dl engthofmlg Tat oT
i ILand
thesloe
pc oerncientAar ere
adL I
),catc
ulatedbyus ingEqs( 22)and( 27)
300 FUJHETAL

Tntheslml
larcas
ewhereLi sglV
enbutRLI
Sunknown,1
tlSnecess
arytO
cal
cul eR
at L.byagraphi
calmethodorbyacomput
ermethodeTnPl
oylng
Eq( 27)Fl
gure31 Satypi
calexampl
ewhereRLisre
ada ga)
nstaglYen
ueor
val L/
H.

CONCLU$1
0N

Af undament alequat i
onf ornow bal anc el nl SOtOpeS eParatlOnby
chromat ogr aphy wa sr or mulated bas ed on t he conc eptorr e l
ati
ve
moveme ntofi s
otop
esl nt hee nnchmentanddl f
ruslOnpr OCeSSeS･
ByI nt roduclngtllequaS l･
Steady･
statemode lorc ons t
antpr oduc t
ion
rl
ow,t hef undament ale quatlOnWasS OIve df T
ornons te
ady- st
atei s
otop
e
accumul atl
Onat( her TOntboundar yre g l
OnOradl SPlaceme ntml grati
on.
TTleequat iondeTIVedc anc overawi der angeorde greesoH s otope
enhchment
Themat hematlC
alt r
eat mentswer ee xtende dtof T
I
nd t her elat
10nS
betweent hes l
opecoef fi
cientAandHETP, be we
t ent heml graLI
Onl ength
Landt heT Tl
aXlmume nrichme ntdegreeR L, andbe tweenRL andt hewl dth
orLhee nnche dpart W.
Thev alidit
yortheder i
vallonwasas c erl alnedbyt hea pplicat
ioT10rthe
denvede quationst o cxLPenment aldat ar epottedr o√bor on isotope
separ
at lOn by di s
pl acementanl On･ eXChange c hromat ography The
HETPort lleexperi
ment alsy st
em ex aml nedwascal cu l
atedt obe01 8
cm

APF
IENDIX

tl T
oc onsj
deTt hedlr
ruSI
OnOlenr i
chedl S
OtOpe
S,Wei nt
roducethe
conceptorrel
ati
vedlrf
.
us1
0mbe t
weenisotope
sAandB r nthesameway
aslnt hedenvatl
OnOrFI Ck'
Slawh t hethermodynamicsofir
reve
rsi
ble
proc
es se
s,westartwlt
hthec hemlCalpotent
ial
soflsot
opes

pA= pま+R' nCA,

Tl L
JB= P
O
B+R'Tl
nCB (
A-1
)

whereR'1
St hegascons
tantandTist
heabs
olut
etempe T
atuT
e.Taki
ngB
astheref
erences t
aternat
edal
,theche
i calpot
m ent
ialorA t oBIS
gl
VenaS

L
I ,=P文一 P
A/ O
B+R'Tl
nCA
/CB (
A-2)
l
soTOPESEPARATI
ON8YDI
SPLACEMENTCHROMATOGRAPHY 381

Thedr
ivL
ngf
orc
eordi
rr
usL
Onf
ort
hlSpr
oce
ssi
sexpr
ess
edas

F = -dp/
dx (
A-3)

a
ndt
henuxof
-dl
rr
uS0n,￠D,1
1 Sexpr
ess
edas

￠L
, IOCAF (
A-4)

wher
eoi st
hernobi)t
tyort
hegi
venspeci
es
Sincet
heproductOfo,R'andTI
, Sequalt
othedi
mlSi
onc
oel
fi
cle
ntOr
t
hlSpr
ocess
,D,weobt al
nthebll
ow川gdi fr
us1
0nnuX･

￠D= -DCB
d(CA/
CB)
/dx (
AI5)

71Equat
10n(15)i
sint
egr
ate
dbe
twe
ent
hes
tar
li
ngpol
ntX=0a
ndt
he
ml
grat
lOnr
TOntendx-L

I
:(R -Ro
,dx -iL# (
1 .+([-Ro,
nI g-

-1
nll- (1- Ro
)ge ALl) (
A-6)

Equat
ion(
9)Indicat
esthatt
het
erm gekLontheriht
g -handsi
deofEq.
A･
( 6)l
Spract
ical
lyzeroatxI0.Regardl
ngtheInt
egralof
Lt
helef
t-
hand
i
sde,wec
anma
keus
eort
hewe
)I-
knowne
quat
ionus
edt
ode
ter
mlnet
he
s]
ngl
e-s
tag
ese
paT
al1
0nfac
torS,Ors
epar
at】
onc
oemc
iente
,fi
rstder
ive
d
bySp
eddi taI(
nge I)
･

￡≡Sl I=∑C.
-
V.
(RIR.
)/QRo
(11月｡
) A･
( 7)

whe r
eIdenotest her ra
ctlOnnumber ,7,i
sthev olumeort heE ractl
On ,CI S
tot
alconcentTatlOnOr- SOtOpeS,andQI Sthet otalefTectj
vet on- e
xchang e
capaclt
yOfthei sotop
e streated.Thl Sequat ionWasi nit
iallyder ive
dF orthe
sys
tem whe ret hes cpar at】
Onc olumnl engthi sf ixedandani sotope
analyst
sWa sdoneont heemue nte r
nerglngf 'T
Om t hec olumn.Ont he
basisoradl rrerentC onc eptOrl SOtOplCml gratlOni nahomog er
LeOuS
me um,
dl Kaklhanade nv edthes aTTletypeore qua tl
OnaSEq( A-7)forthe
syst
em wTle
rei sotopedlS tnbut1
0† 1int heml gratl
Onme di um i sknownby
dlr
e C
tSampllng( /6)T nthi scas
et heamountori sot
opesi nt hemi gration
me dl
uml Susedi ns t
eadoft heamountl nthee muent ,expr e
s s
e dbyC, -
V
, n
i
Eq･(A･7)
 Wben t
hetotalconcent
Tat
lOn OrlSOt
OP eSISCOnSLantthr
oughoutthe
r
nlgr
ati
on band and t
hesamp】lngwi dth- ∼suff
ici
entl
y narr
ow,thati,
s
C ,
i
i
,-C
o
ArandQ CJ･ =
,Eq.(A-7)isrearrangedto

(
R - R.
)dx/
LRo
(1-Ro
) (
A-8)
Jo
Combl
njngEqs
･(A- A-
6)and( 8)
,weobt
ain

g= ( /(1- R｡
e郎 oL - 1) )

REFERENCEi

/ F H Spe ddl 叩.IE Powe lLandH ISv ec J Am Che m Soc 7 7,6125()95

5)
2 E Gl uec kaufJ, a
ns FoT OdL7ySot.jJ ,34( )
95 5)
3 E Gl uec kaul.lnSepa, alOn0
l /hol op eS(H London.e d).Nc -e ss.London,19
61.pp
2
09-24 8
4 H Kak Jhana .T 01,andT Nomur aJ NuC /S° ∫Te c
h170/.]4､572(1977)
5 H Kak lhana.Sep Sc JT echnoL .]
5.587( 198 0)
6 SFu )ne
l .JbE
d.17 .】049( t9 82)
7RJ ac ques JbJd./5.533( 1980)
8 EGi l
rdandA_Cal usaru,Isorope
npr mS
( .13,1 74(1977)
9 Z Ha glWar aandY Tak ak ura.INUB /ScLT e
ch10I
7 .6,3 261t96
9 1
1
0 PConr ar d.M Caude .arLd氏 Ros set,Se)Sc
J l,7,465( 1972)
I
J PCohT ar dan dR Ros sct､IbJd 7, 48 7(1972)
/
2 SF u J
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