Indian Journal of Chemistry

Vol. 30A, June 1991, pp. 531-535

Separation of boron isotopes by ion exchange chromatography

B K Sharma* & R Subramanian
Chemical Technology Section, Indira Gandhi Centre for Atomic Research, Kalpakkam, India
and
PKMathur
Water and Steam Chemistry Laboratory, Applied Chemistry Division, BARC, IGCAR Campus, Kalpakkam, India
Received 14 September 1990; revised and accepted 4 February 1991

Separation of the isotopes of boron by ion exchange chromatography has been studied using
mannitol as a complexing reagent for boric acid. Quadratic regression analysis shows that ~e pH
and the acidity constant (pK.) of 0.1 M boric acid can be related to the concentration of mannitol,
[m], by the relations:

pH = 5.365 - 9.270 [m] + 11.869 [m]2

pK. = 9.124-13.684 [m] + 14.482 [m]2 for 0.0 ~[m]~ 0.5

The values of the single stage separation factor for lOB_liBexchange are found to be 1.0173 and
1.0194 for 0.1 M boric acid in presence of 0.1 M and 0.2 M mannitol. The value of separation fac-
tor for 0.2 M mannitol is similar to the one obtained by reduced partition function ratios for the
reaction, IOB(OHh+ lIB(OH)i ~ IOB(OH)i+ lIB(OHh, indicating thereby that lOBis enriched in the
anionic species. The effects of mannitol concentration on the breakthrough profiles and separation
factor have been studied. The effect of concentration of boric acid (at constant mannitol concentra-
tion of 0.3 M) has also been studied for the resin used. The advantages of mannitol over glycerol are
discussed.

Boron is known to have two stable isotopes, viz.,
lOBand 11 B with the natural abundance of lOBbe-
ing 19.8 atom%. The thermal neutron absorption
cross-sections for lOBand liB are 3837 and 0.005
b~m respectiv.ely whereas natural boron has the
absorption cross-section of 752 bams. Because of
its higher neutron absorption cross section, l.oB
enriched in some specific compounds is used for
reactor control, neutron fluence monitoring, neu-
tron shielding, neutron counting and neutron the-
rapyl,2.
Separation of boron isotopes has been reported
by fractional distillation, chemical exchange distil-
lation, photo-dissociation of specific .compounds,
and ion exchange chromatography3'7. -Fractional
distillation and chemical exchange distillation
methods have limitations due to (a) the require-
ment of operation at low temperature and re-
duced pressure, (b) associated corrosion problems
and (c) irreversible decomposition of the feed ma-
terials and their toxic nature. Although photo-dis-
sociation method gives relatively high values of
separation factors (~= 2 for lOB separation), only
small amounts of highly enriched material can be
produced in addition to certain other limitations.
After the original proposal by Martin and Syn-
ge8, several workers have studie<t the separation
of various isotopes by ion exchange chromatogra-
phy. Because of various inherent advantages of
ion exchange chromatography5, it has become
possible to use the technique for large scale sepa-
ration of various isotopes3• Using Amberlite CG-
400-1 anion exchange resin in hydroxyl form,
Yoneda et aU 9btained the single stage separation
factor values of 1.010 and 1.0166 respectively for
the separation of boron isotopes in the absence
and presence of glycerol. The increase in separa-
tion factor in the latter case was attributed to the
increased acidity of the boric acid. Rossett et aL4
and Kakihana f?t a/.6 have studied the separation
of boron isotopes using strong base anion ex-
change resin. It was found4 that the value of se-
paration factor decreased with an increase in the
concentration of boric acid in the aqueous phase.
This decrease in the value of separation factor
was attributed to the formation of polynuclear

531
 INDIAN
complexe$ of boron called polyborates. The poly-
borate fotmation takes place because of Donnan
invasion9 i of boric acid, a weak electrolyte, and
can be avoided by enhancing its ionization. Ioni-
zation ca* be increased by using considerably di-
lute solujtions, but employing dilute solutions
means higher operational costslO. Thus, some
other me*ns such as complex formation has to be
adopted fpr achieving increased ionization of bor-
ic acid. J)artusek et a/.ll found that the formation
constant pf boric acid-mannitol complex is much
highe:r th~n that of boric acid - glycerol complex.
This suggests that mannitol might be a superior
reagent t<)lglycerol for the separation of boron is-
otopes. 11he present study was undertaken to in-
vestigate this in depth and the results are reported
in this pal1>er.
Material~ and Methods
AR gr~de chemicals were used in this study.
Conducti~ity measurements were carried out at
22.0 ± O.rC by using a Philips PP 9042 transmit-
ter coupled with an Agronix digital panel meter
and a tetnperature sensor Pt-lOO. The cell con-
stant of the cell used was 1.01 em - 1. The demin-
eralized ~ater used in the study had a specific:
conductivity of 1.51 IlS/cm at 22.0 0c. Boric acid
(100 ml, 0.1 M) was taken in a double wallod ves··
sel and ~annitol solution of appropriate concen··
tration (0.55 M) was added from a burette; con-'
ductivity of the resulting solution was measuredl
r plete isotopic exchange. This resin was then trans-
after mi,qing the two solutions thoroughly. In an··
other experiment, the above procedure was re··
peatl~d ~sing glycerol instead of mannitol. Solu··
tions were thoroughly mixed by stirring with a
magnetic: stirrer throughout the measurements.
The sa~ procedure was followed for pH-metric
measure~ents also.
T~ble I - Characteristic properties of the resin
(Tulsion A-n MP)
Type : Strongly basic (type I)
Chemical Clomposition Polystyrene macroporous
Active gro~ps R-N(CH,)PH
Degree of ~ross-Iinking
Beads
Physical form
Appmx. sdreen grading :Z0-50 mesh USS
Moisture cbntent : 41')';,
Total capahty : 1.0 meq/ml
pH range i : 0-14
Vana:lion Ofvolume : CI to OH form: 9.03'X,
OH - to borate form: 1.0°;;,
532
'I
J CHEM, SEe. A, JUNE 199-1
Ionization constant was determined by the pH-
metric titration method. pH measurements were
carried out using a Metrohm titroprocessor. The
electrode was calibrated using potassium hydrog-
en phthalate (pH 4.02), phosphate (pH 6.68) and
borax (pH 9.18) buffers ..
An indigeneously manufactured Tulsion A-27
macroporous strong base anion exchange resin
(see Table 1) was used in this study. Chemical an-
alysis of boric acid was carried out by titration
against standard NaOH solution after addition of
mannitol, and its isotopic analysis for lOB/liB ra-
tio was carried out by using a Vg Micromass 30
BK mass spectrometer having a thermal ioniza-
tion chamber and a Daly detector. lIlB/lIB ratio
was determined by measuring the peak heights at
mass numbers 88 and 89 for sodium memborate
ions containing lOB and liB atoms respectively,
produced by thermal ionization of N azBOz.
To determine the separation factor by the batch
method the resin in hydroxyl form (10 mI) was
taken in a 125 mI stoppered flask. To this was
added 25.0 mI of 0.1 M boric acid solution con-
taining the required amount of mannitol. The so-
lution was equilibrated for 10 min with intermitt-
ent shaking of the contents and then the super-
nate was discarded. Again 25.0 mI of the fresh
boric acid solution was added. The above proce-
dure was repeated 20-25 times to ensure com-
ferred to the glass column, washed with deminer-
alized water and eluted with 0.1 N HCI. The ef-
fluent was collected and analysed for isotopic
composition by using the mass spectrometer.
In a dynamic method, the single stage separa-
tion factor was determined by the technique of
frontal analysis. A· wet resin slurry in hydroxyl
form (100 mI) was taken in a glass column (int.
dia. of 18.1 mm). Feed boric acid solution (0.1 M)
containing the required concentration of mannitol
was passed through this column at a constant flow
rate of 2.7 ml/min. After the boric acid break-
through, effluent samples of predetermined vo-
lumes were collected. The feeding of the boric ac-
id solution was continued for a sufficient length of
time so as to ensure the complete isotopic ex-
change. The collected samples were analysed
chemically for boric acid content and isotopically
for lOB/llB ratio.
Results and Discussion
The process of boron isotope separation by ion
exchange chromatography can be summarised in
terms of the following three steps.
 SHARMA el af.: SEPARATION OF BORON ISOTOPES

(A) Loading of the resin by mannitol-borate com-
plexanion
R - OH + BMH ....•R - BM + H20
(B) Displacement of the band with He/;
In this case two reactions occur: (i) chemical ex-
change at the front boundary (i.e. reaction (A))
and isotopic exchange reaction throughout the
band, i.e.,
and (ii) at the rear end of the band,
R - BM + HCI ....•R - CI + BMH
(C) Regeneration of the resin to hydroxyl form:
R - CI + NaOH ~ R - OH + NaCI
where R represents cationic resin network and
BMH represents mannitol-boric acid complex.
The reactions (A) and (B) are fast and favour-
able because: (i) the affinity of the anion exchange
resin is higher for the mannitol-borate complex
compared to that for the hydroxyl ions, (ii) the af-
finity of the resin for chWflde ions is higher com-
pared to that for the mannitol-borate complex\
and (ill) H+ ions and mannitol-borate anions as-
sociate to form less dissociated acid, and H + and
OH- ions neutralize to yield water.
Since the single stage separation factor has been
found7 to increase with the increase in the acidity
of the boric acid, an attempt was made in the
present study to increase the acidity of boric acid
by addition of mannitol as a complexing reagent.
The increase in acidity was monitored by record-
ing the conductivity of 0.1 M boric acid after the
successive addition of appropriate amounts of
mannitol solution and the values were compared
with those obtained with glycerol under ident-
ity of a boric acid solution upon addition of man-
nitol can be considered to occur in two steps: the
ionization of boric acid, BH ~ H+ + B -, followed
by formation of some complex(es) upon addition
of mannitol, B - + nM ~ BM;. The oveIall reac-
tion .as monitored by conductivity measurements
can be written as:
BH + nM ~ BM; + H+ ... (1)
According to the above reactions, formation of
complex anions takes place alongwith the release
of H+ ions; therefore, the conductivity of the sys-
tem increases considerably as the complex forma-
tion takes place, the increase in conductivity being
much more in the case of mannitol compared to
that in the case of glycerol. pH measurements
were also carried out to monitor the release of
H+ ions during the complex formation. The dec-
rease in pH was much more in the case of manni-
tol addition compared to that in the case of gly-
cerol. A quadratic regression analysis showed that
for 0.1 M boric acid, pH of the solution could be
related to the concentration, [m], of mannitol by
the equation:
pH = 5.365 - 9.27 [m] + 11.869 [mJ2 ... (2)
where 0.0 ~ [m] ~ 0.5.
To see the effect of mannitol concentration on
the increase in the ionization constant of boric ac-
id, solutions of boric acid containing different
10·00
.,.0 8.00
""

ical conditions. A drastic increase in conductivity

of the solution was observed on the addition of
mannitol whereas the increase with the addition
7,00
of glycerol was not that much appreciable.
It is reported12 that cis-diols fOfQl 1:1 and 2:1
mole ratio complexes with borate ion. The 1:1
complex is formed with the removal of two water 6·00
molecules in a reaction between a polyol mole- 1
cule and a borate ion, while the 2:1 complex is 5.001 I I I I I I
formed by the removal of four water molecules in o 1·0 2·0 3'0 "'0 S-O

MOLE RATIO OF MANNITOL TO BORON

a reaction between two polyol molecules and a
borate ion. It is established12 that mannitol (M) Fig. 1 - Ionization constant of 0.1 M boric acid at different
reacts only with borate (B -). The increase in acid- mannitol to boron ratios.

533
 INDIAN J CHEM, SEC. A, JUNE 1991

concentr*ions of mannitol were prepared and
ionizatiori constant of the mannitol-boric acid
complex r-vas determined using the pH-metric ti-
tration ~thod. The values so obtained are pre-
sented inl Fig. 1. It can be noted that the pKa of
the manriitol-boric acid is related to the concen-
tration ofimannitol by the relation,
pK. ,= 9.1~4 -13.684 [m] + 14.482 [mF ... (3)
where 0.0 ~ (m] ~ 0.5.
The islotopic exchange separation factor was
determinfd by the method described by Kakihana
where Xr and Xs are the mole fraction of lOB in
the resin and solution phase respectively. The da-
ta obtained are ploited in Fig. 3 which shows that
the separation factor decreases as the concentra-
tion of boric acid is increased at constant manni-
tol concentration. This is in consonance with the
observation of Rosset et al.4• However, the effect
is less pronounced compared to that observed by
these authors in the case of pure boric acid indi-
cating thereby that polynuclear complex forma-
20·00

et al.6• F~om the experimentally obtained data fot"

0.1 M i boric acid in presence of 0.1 M
and 0.2 M mannitol (Fig. 2), the values of
r
19·80

separatiob factor were determined by the equa··

tion, ,~rn
...
K = 1.0 + Ci.Yi.(Ro - Ri) o
... (4) •• 19·60
Q.Ro.(1.0- Ro) ~
l2
where Yi = volume of the sample collected, ...

Ci = mol~rity of boric acid, Ri and Ro = mole

fractionsl of lOB in the ith sample and feed solu- MANNIlOL=0·1M *-*
MANNITOL = 0·2M -IJ-O-
tion resPectively, and Q = capacity of the resin co-
lumn ..
The sfparation factor values obtained (1.0173 19·20

and 1.0~94) are higher compared to the reported

value of! 1.0166 obtained in the case of glycerol
addition'to boric acid7• The value of separation
factor iq presence of 0.2 M mannitol is compar-
able to t.he one calculated based on the reduced
partitioJ function values2 for the reaction,
19'00L
o 30-0
me11N
L-..-LI
60,0
EFFLUENT,".
I

Fig. 2 - Breakthrough profiles during loading of the resin with

0.1 M boric acid containing (A): 0.1 M mannitol and (B): 0.2

1·021
Mmannitol.
I
90-0
COLUMN CAPACiTY
I t

120.0

,
IOB(OH)b+ llB(OH),;- ;=!. lOB(OH),;-+ IlB(OH)3
.... (5)

The breakthrough becomes sharper and the

front bo~mdary is more depleted of the lighter is- '019

otope $ the concentration of mannitol is in-

creased;. this leads to the enrichment of lOBin the
anionic species in the resin phase. This also con-
a:
firms th~ effect of mannitol on the separation fac- u 0
w If)
a:
4:
if~
i= 1·017
1·015
Z
tor, i.e.,! the isotopic equilibrium is reached fast~:r
when K, is higher. Hence, with the increase in the
concenttation of mannitol the value of the singIe

ment with
stage separation
the increase
factor increases.
in ionization
Thisofisboric
in agree-
acid
as confirmed from ionization constant measure-
ments (Fig. 1).
The Mfect of concentration of boric acid on se- 1·013
paratiod factor was determined by the batch
methodP. The mannitoi concentration was fixed
at 0.3 M. The value of separation factor was cal- "0'" I I I I I I I I I I
o 0·10 020 0 ·30 0,40 0·50
culated!by the equation:
CONCENTRATION OF BORIC ACID,M

Xr.q -Xs)
K=--L~--- ... (6) Fig. 3 - Variation of separation factor with concentration of
(1-'" Xr). Xs boric acid.

534

11II1''1111,,"''1 !
 SHARMA et al.: SEPARATION OF BORON ISOTOPES
1'020
0: a:
f2 u
~
w
1Il 1·016
i5
~ ,,014
1·012
1-
1'OlOf I I I I
o 0·6 1·2
MOLE RATIO OF MANNITOL
Fig. 4 - Variation of separation factor for 0.1 M boric acid at
different mannitol to boron ratios.
tion is less pronounced in the present case. The
observed higher value of the isotopic exchange se-
paration factor in the presence of mannitol com-
pared to that reported by Yoneda et al:13 in the
presence of glycerol indicates that the formation
of polynuclear complexes of boron in the present
system is much less pronounced. This may be at-
tributed to the higher tendency of mannitol to
form 1:1 complexes with horate anions by decom-
posing the polyborate anions14•
The effect of mannitol: boron ratio on the se-
paration factor has been studied by the batch
method13• The separation factor increased15 as
this ratio was increased from 0 to 2.0. Beyond
this value no appreciable effect was observed by
increasing the concentration of mannitol (Fig. 4).
This behaviour may also be attributed to the
tendency of mannitol to form 1:1 and 2:1 mole
ratio complexes by decomposing polynuclear bor-
ate anions.
Apart from achieVing the higher value ,of iso-
topic exchange separation factor in this process
by using mannitol as the complexing reagent, fol-
lowing are the distinct advantages of this process:
(i) Similar increase in ionization constant of
boric acid can be obtained by a very small con-
centration, viz., 0.10 M of mannitol compared to
the requirement of 1.62 ·M glycerol. Mannitol be-
ing a solid, requires no storage facilities as re-
quired in the case of glycerol and the required
amount can be accurately weighed and directly
added to the boric acid solution.
(ii) Because of higher value of isotopic ex-
change separation factor, the breakthrough pro-
files are sharper and isotopic equilibrium is
reached faster.
(ill) The problem of polyborate formation is re-
duced because of the tendency of mannitol to
form 1:1 complex with the borate anion by de-
composing the polynuclear ions to mononuclear
ones 14.
Acknowledgement
The authors are grateful to Shri S R Paranjpe,
Director, IGCAR for his keen interest during the
I ~ I J
1·8 2·4 J·O course of the present· investigation and to Dr.
TO BORON
c.K. Mathews, Head, Radiochemistry Programme
for providing necessary facilities for isotopic ana-
lyses.
References
1 Sharma B K, Subramanian R & Mathur P K, Indian J
Chern, 30A(1991)66.
2 Kakihana H, Kotaka M, Satoh S, Nomura M & Okamato
M, Bull chem Soc Japan, 50 (1977) 158.
3 Sharma B K, Separation of boron isotopes by ion ex-
change chromatography, M. Phil. Disser., Punjabi Uni-
versity, Patiaia, 1986.
4 Rosset R, Fould H, Chemla M, Labrousse H, Hure J &
TremillonB, Bull Socchim France, (1964) 607.
5 Tremillion B, Bull Soc chim France, (1958) 502.
6 Kakihana H & Aida M, Bull Tokyo Inst Tech, 90 (1969)
77.
7 Yoneda Y, Uchijima T & Makishima M, J phys Chern, 63
(1959) 2057.
8 Martin A J P & Synge R L M, Biochem J, 35· (1941)
1358.
9 Riemen W III & Walton H F, Ion exchange in analytical
chemistry (Pergamon Press, New York), 1970,30.
10 ChakrabortyT, Rep RCS/BT-4 (1980).
11 Sprta F & Bartusek M, Chemia, 3 (1973) 91.
12 KnoeckJ & Taylor) K,Analyt Chern, 41 (1969) 1730.
13 Sharma B K & Subramanian R, Symposium' on radi-
ochemistry & radiation chemistry, IGeAR, Kalpakkam,
1989, paper ST-03.
14 Paal T, Acta chem hung (Budapest), 91 (1976) 393.
15 Sharma B K, Subramanian R & Mathur P K, Symposium
on radiochemistry & radiation chemistry, Nagpur, 1990,
. paper AL.41.
535