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Zinc Isotope Fractionation on Benzo-15-crown-5
Resin by Liquid Chromatography
Xingcheng DING
a
, Masao NOMURA
b
& Yasuhiko FUJJI
b
a
Institute of Nuclear-Agricultural Sciences, Zhejiang University , Hangzhou , 310029 ,
China
b
Research Laboratory for Nuclear Reactors , Tokyo Institute of Technology , O-okayama,
Meguro-ku, Tokyo , 152-8550 , Japan
Published online: 05 Jan 2012.
To cite this article: Xingcheng DING , Masao NOMURA & Yasuhiko FUJJI (2007) Zinc Isotope Fractionation on Benzo-15-
crown-5 Resin by Liquid Chromatography, Journal of Nuclear Science and Technology, 44:4, 623-627
To link to this article: http://dx.doi.org/10.1080/18811248.2007.9711850
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Zinc Isotope Fractionation on Benzo-15-crown-5 Resin
by Liquid Chromatography
Xingcheng DING
1;
, Masao NOMURA
2
and Yasuhiko FUJII
2
1
Institute of Nuclear-Agricultural Sciences, Zhejiang University, Hangzhou 310029, China
2
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology,
O-okayama, Meguro-ku, Tokyo 152-8550, Japan
(Received July 21, 2006 and accepted in revised form January 22, 2007)
)
2
. Due to the short-
ened radius of dichloro complex compared with aqua solu-
tion, it may lead to the large adsorption of zinc chloride
on resin phase. In Table 2, there was adsorption capacity
in 1.0 mol.dm
3
HCl solution larger than that of the present
work although zinc chloride concentration was smaller than
that of the present work. Such kind of large zinc adsorption
could be considered as the contribution of the chloride ion
concentration. Zinc adsorption on resin phase was so compli-
cated that it could not be explained only by anion concentra-
tion. When compared with the results obtained by organic
solvents in Table 2, acetone solvent exhibited the largest
adsorption capacity among them. It may be aected by the
dielectric constant of dierent organic solvents.
19)
Zinc ad-
sorption capacity changes with an dielectric constant and
usually large dielectric constant organic solvent had small
zinc adsorption capacity. In methanol and ethanol solvents,
there were small amount of complex species between zinc
ion and these two solvents, and zinc mainly make complex
with crown ethers. Since ethanol solvent had a smaller di-
electric constant than methanol solvent, it has large adsorp-
tion capacity. While, to acetone solvent, acetone had the
smallest dielectric constant among the solvents in Table 2,
zinc ions could make complex both with crown ether and
acetone solvent, and it led to the largest adsorption capacity.
When compared with the eect of anion chloride concentra-
tion and dielectric constant in case of Refs. 15) and 17)
in Table 2, Zinc adsorption capacity in 1.0 mol.dm
3
HCl
had relatively smaller adsorption capacity than the result in
acetone solvent, although 1.0 mol.dm
3
HCl had a much
smaller dielectric constant value, it means an anion chloride
concentration has much larger contribution to zinc adsorp-
tion capacity than that of a dielectric constant. According
to the experimental results,
18)
distribution coecient of zinc
in acetone solution was 1.0, and this means zinc and crown
ether can easily make complex with the ratio of 1:1; While
the distribution coecient in ethanol solution was only
0.3, it indicates that zinc is dicult to make complex with
crown ether in ethanol and has small adsorption capacity.
A large distribution coecient value means large zinc ad-
sorption capacity and zinc can easily make complex with
crown ethers.
2. Zinc Isotopic Eect Observed on Frontal and Rear
Bands
The zinc concentration breakthrough prole was plotted in
Fig. 1. The breakthrough volume of ve meter zinc chroma-
tography was equal to 212 ml, and, after this volume, a sharp
increase in the zinc concentration was observed, showing
the formation of a self-sharpening frontal boundary. This
means the ideal displacement chromatography was obtained
at a frontal band. The at shape was kept before the decrease
of zinc concentration when the feed solution was changed to
ethanol solution. The shape of a rear band was far away from
sharpness and could not form ideal displacement chromatog-
raphy at presently condition. It indicates the desorption be-
havior of zinc on resin phase is dicult only by ethanol sol-
vent. Further experiments are needed in order to nd out the
best solvent for ideal displacement chromatography at a rear
band. However, the present results proved that adsorbed zinc
can be completely eluted out by ethanol solvent.
A zinc isotopic ratio of the present ve-meter experiment
was depicted in Fig. 2. The isotopic ratio data of a fraction is
expressed as the enrichment ratio, , and is dened as
Eq. (2):
H
Zn=
64
Zn
i
H
Zn=
64
Zn
o
; where H 66,68: 2
where the superscript H is the value of heavy zinc mass
number 66 or 68, the subscript i and o denote the euent
fraction number and original feed solution, respectively.
The denition can be expressed as an isotopic ratio in a local
fraction sample divided by the corresponding ratio in the
feed solution. Isotope fractionation of zinc isotopes occurred
within 12 ml range from the breakthrough point at the frontal
band, while in a rear band, zinc isotope fractionation hap-
pened in a large volume range. To each local fraction, the
enrichment ratio was a monotonous decrease with the eu-
ent volume. The results that the enrichment ratio value was
larger than 1.000 in the frontal band indicated that the heav-
ier isotope of zinc was preferentially fractionated into the
eluted samples; On the contrary, it was proved that the light-
Table 2 Zinc adsorption capacity in various chromatographic operation
Solution
Zn con. Dielectric Temp. Q
tot
Reference
mol.dm
3
constant
a)
K mmol
1.0 mol.dm
3
HCl 0.05 4.6 313 0.94 17)
Acetone 0.46 20.7 298 12.2 15)
Methanol 0.09 32.6 298 0.09 18)
Ethanol 0.08 24.3 323 0.39 This work
a)
The value of dielectric constant was measured at 20
3
where the subscripts i and o denote the euent fraction num-
ber and the original feed solution, respectively; S is the sep-
aration factor; c and V are zinc concentration (mol.dm
3
)
and volume (ml) of each euent fractions, respectively; R
is the atomic fraction of isotopes and Q
tot
is the total amount
of adsorbed zinc on resin phase (kmol). The summation in
Eq. (3) has taken place in all fractions in which isotope frac-
tionation was observed.
Table 3 tabulated the results of separation coecient and
separation coecient per unit mass dierence of zinc for
both the frontal and rear bands. The separation coecient
value for
68
Zn/
64
Zn was 5:26 10
4
in the frontal band.
Separation coecient of the frontal band has larger value
than that of the rear band for both two isotopic pairs. When
compared with the separation coecient per unit mass dif-
ferent, the frontal band has much larger deviation than that
of the rear band. The reason may be due to the large euent
volume of the rear band. The separation coecient value ob-
tained in this work was only half than the value which per-
formed on DC-18-crown-6 resin,
9)
but larger than what was
obtained by microporous strongly acidic cation exchange
resin.
22)
The value of this work agreed with the value by
the same type crown ether which was obtained in 1.0
mol.dm
3
hydrochloric acid solution by Oi and his
group.
15,16)
IV. Conclusions
The chromatographic fractionation of zinc isotopes was
performed on the synthesized benzo-15-crown-5 resin in
the breakthrough manner both for the frontal and the rear
bands at 323 K. Zinc chemical species in solution and zinc
adsorption capacity on resin were so complicated and it
may relate to the anion chloride concentration and solvent
dielectric constant. Anion chloride concentration has a larger
eect on zinc adsorption capacity than that of a dielectric
constant. Zinc adsorption capacity in the present study was
smaller than that in acetone and 1.0 mol.dm
3
hydrochloride
solution. It was rstly reported that heavier zinc isotopes
were found enriched to the solution phase and lighter zinc
isotope was concentrated on the resin phase. The isotope
separation coecient for isotopic pair of
68
Zn/
64
Zn for the
frontal and the rear bands, were around 5:3 10
4
, 4:5
10
4
, respectively. Separation coecient per unit mass dif-
ference of zinc in the frontal band was larger than that of
the rear band.
Acknowledgements
The present work was performed as a part of Innovative
and Viable Nuclear Energy Technology Development Pro-
ject, The Institute of Applied Energy, Japan.
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Zinc Isotope Fractionation on Benzo-15-crown-5 Resin by Liquid Chromatography 627
VOL. 44, NO. 4, APRIL 2007
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