N ,N ,N ,N-TETRABUTYLSUCCINYLAMIDE FROM NITRIC. ACID SOLUTIONS. You-Shao Wang, Chao-Hong Shen, Yong-hui Yang,. Jian-Kang Zhu, Bo-Rong ...
Jointly published by Elsevier Science S. A., La:tsonne and Akadlmiai Kiad6, Budapest
J. R a d i o a n a l . Nucl. Chem. ,Letters 213 (3) 199-205 (1996)
S O L V E N T E X T R A C T I O N OF T H O R I U M ( I V ) ION W I T H N ,N ,N , N - T E T R A B U T Y L S U C C I N Y L A M I D E FROM NITRIC ACID SOLUTIONS
You-Shao
Institute
Wang, C h a o - H o n g Shen, Y o n g - h u i J i a n - K a n g Zhu, B o - R o n g Bao
Yang,
of N u c l e a r
P.O.
Research, C h i n e s e A c a d e m y Sciences Box 8 0 0 - 2 0 4 S h a n g h a i , China
Received Accepted
26 M a r c h 5 April
of
1996 1996
It was found that N , N , N , N - t e t r a b u t y l s u c c i n y l a m i d e (TBSA) in a d i l u e n t c o m p o s e d of 50% 1 , 2 , 3 - t r i m e t h y l b e n z e n e (TMB) and 50% k e r o s e n e (OK) can e x t r a c t thorium(IV) ion from a n i t r i c acid solution. The r e s u l t s of the e x t r a c t i o n study s u g g e s t e d the formation of a 1:4:1 thorium(IV) ion, n i t r a t e ion and N , N , N , N - t e t r a b u t y l s u c c i n y l a m i d e complex as e x t r a c t e d species. The r e l a t e d therm o d y n a m i c f u n c t i o n s w e r e a l s o calculated.
INTRODUCTION
Substituted have pound
been
alkylamides
reported
contains
ing a b i l i t y
in m a n y
strongly -
\
as e x t r a c t a n t s papers I-3.
polar
for metal
cations
0236-5731/96/US $12.0 Copyrighf 9 1996 Akaddmiai Kiad6, Budapest All rights reserved
199
for a c t i n i d e s
This
C=O groups. is s i m i l a r
k i n d of comTheir
chelat-
to those
of
WANG et al.: SOLVENT EXTRACTION OF Th(IV)
extractants
containing
phosphorus.
contain
no p h o s p h o r u s
produce
new solid w a s t e
cinerable. products
(carboxylic
tractants
[HNO3],
They
discusses
[Th4+],
ing a b i l i t y reaction
[TBSA]
they
considered
dium by T B S A
are not h a r m f u l
of n u c l e a r
systematically
and the r e l a t e d
ex-
fuel.
the e f f e c t s
and t e m p e r a t u r e
of thorium(Iv)
in-
degradation
as p o t e n t i a l
of T B S k for t h o r i u m ( I V ) .
mechanism
which
they do not
are c o m p l e t e l y
and amines)
for the r e p r o c e s s i n g
paper
compounds
and h y d r o l y t i c
acids are
The
are i m p o r t a n t ;
because
The r a d i o l y t i c
to the process.
This
atoms
of
on the e x t r a c t -
The e x t r a c t i o n
from n i t r i c
thermodynamic
acid me-
parameters
are p r e s e n t e d .
EXPERIMENTAL
T B S A was The p u r i t y emental
synthesized
of the d i s t i l l e d
analysis,
of the p r o d u c t procedure which
was
as follows: a certain
shaken with
ing a g i v e n
with
The
composed
was
The p u r i t y
A typical
extraction phase
amount
ion and
of thorium(IV)
of T B S A
a suitable
for
nitric
by of 50%
Samples
immediately
after
phase
thorium(IV)
ion was d e t e r m i n e d
coefficient
98%.
by el-
0.5 ml of the a q u e o u s
and 50% kerosene.
mA spectrophotometric
checked
I ml of the o r g a n i c
concentration
preequilibrated diluent
was
spectroscopy.
than
et al. 4
to S t a n l e y
product
IR and NMR
was h i g h e r
contained
HNO 3 was
according
of both
phase
10 min, acid
containwhich
was
solution.
1,2,3-trimethylbenzene phases
separation.
were
analyzed
The c o n c e n t r a t i o n
of
by the c h l o r p h o s p h o n a z o -
m e t h o d 5, and then ~ the d i s t r i b u t i o n
of thorium(IV)
ion was 200
calculated.
WANG et al.: SOLVENT EXTRACTION OF Th(IV)
I0
D
1
0,1
2
3
4
5
6
[HN03], mot. Fig.
I. C o r r e l a t i o n b e t w e e n l g D m h 4 + and [HNO 3] at 25 ~ [Th 4+] = 5 . 2 9 x 1 0 - 3 moi/l, [TBSA] = 0.05 m o l / l
RESULTS
AND DISCUSSION
Figure
I shows
the e f f e c t
HNO 3 on the d i s t r i b u t i o n in the two p h a s e s . concentration thorium(IV) the
shows
increases
that there
petition
of the
concentration
coefficient
Accompanied
of HNO3,
concentration
tion
['1
with
of t h o r i u m ( I V ) an i n c r e a s e
the d i s t r i b u t i o n
is a m a x i m u m ,
of t h o r i u m ( I V )
ions
study.
4 mol/l,
which
ion
in the
coefficient
in the r e g i o n of our
of HNO 3 s u r p a s s e s
of
of
When
the c u r v e
is due to the com-
and HNO 3 for the c o o r d i n a -
sites of TBSA.
Figure
2 illustrates
concentration rium(IV)
on the d i s t r i b u t i o n
ion b e t w e e n
coefficient
the e f f e c t of t h o r i u m ( I V )
the two phases.
an i n c r e a s e
ion until
a concentration 3 indicates
on the e x t r a c t i o n values
increase
of tho-
The d i s t r i b u t i o n
of Th 4+ is an a l m o s t h o r i z o n t a l
line w i t h
Figure
coefficient
ion
in the c o n c e n t r a t i o n
straight of t h o r i u m ( I V )
of 8x]0 -3 m o l / l .
the e f f e c t
of t h o r i u m ( I V }
linearly with 201
of T B S A ion.
The
concentration igDTh4+
the i n c r e a s i n g
concentra-
WANG et al.: SOLVENT EXTRACTION OF Th(IV)
D6
94
I
I
1
Fig.
I
!
3
~
I
I
I
5
7
[Th4+],x
10 -3 mot. [-1
10
2. C o r r e l a t i o n b e t w e e n i g D T h 4 + and ig [Th 4+] at 25 ~ [TBSA] = 0.5 m o l / l ; [ H N 0 3 ] : 3.5 m o l / l
10 D
11
t
t
I
03
,
I
05
i
i
07
1.0
[TBSA],mo[[ -I Fig.
3. C o r r e l a t i o n b e t w e e n igDTh4+ and ig [TBSA] at 25 ~ [Th4+] : 5 . 0 0 x i 0 - 3 mol/l; [HNO3] : 3.5 mol/l
tion of
TBSA,
and the
slope
that
the b i n d i n g
ratio
1:1.
The r e s u l t s
illustrate
is 1.1.
This
of T B S A with
HNO 3 and T B S A are the m a i n
that
th0rium(IV)
shows ion is
the c o n c e n t r a t i o n s
factors 202
result
which
can a f f e c t
of the
WANG et al.: SOLVENT EXTRACTION OF Th(IV)
D6 5
/
-j _
I
I
I
30
3.1
3.2
I 3.3
3.4 I
T,xl0 Fig.
-3
4. C o r r e l a t i o n b e t w e e n igDTh4+ and ~ . [Th 4+] = 5.00xi0 -3 mol/l: [TBSA] = 0.5 mol/l; [HNO 3] = 3.5 mol/l
distribution
coefficient
t r a c t i o n data extraction
indicate
of thorium(IV)
ion. The ex-
that T B S A is e q u a l l y g o o d
thorium(IV)
for the
ion from nitric acid m e d i u m w h e n
c o m p a r e d with TBP and N , N - d i a l k y l a m i d e 6. Figure
4 illustrates
distribution
coefficient
values
increase
result
shows
from the a q u e o u s
ion. The igDTh4+ I This l i n e a r l y with the i n c r e a s e of T" phase
of thorium(IV)
to the o r g a n i c phase
ion
is an exo-
and the e n t h a l p y of Th 4+ e x t r a c t i o n
is
kJ/mol.
In th~se e x t r a c t i o n p h a s e was
studies,
in a large excess
ion in the a q u e o u s phase. 1:4:1
on the
of thorium(IV)
that the e x t r a c t i o n
thermic process -17.56
the e f f e c t of t e m p e r a t u r e
c o m p a r e d with thorium(IV)
The r e s u l t s
c o m p l e x of thorium(Iv)
tracted
The:q)+
4NO3(aq)+
s u g g e s t that a
ion, NO 3- and T B S A was ex-
into the o r g a n i c phase.
r e a c t i o n of the p r e s e n t Eq. (I)
T B S A in the o r g a n i c
Thus,
the e x t r a c t i o n
system can be e x p r e s s e d
TBSA(org)= 203
by
Th(NO3)4.TBSA(org )
(I)
WANG et al.: SOLVENT EXTRACTION OF Th(IV)
Then,
the e x t r a c t i o n
constant
(Kex)
can be defined
as
K
ex =
- - I_ [ N O ~ ]o aq - -a 4 [ T B S A ] _ _ -or I q g
[Th(NO3)4.TBSA]org[Th4+]
and Eq.
(2) can be r e a r r a n g e d
(2)
as
4[T~SA]o~ g
Kex: D T h [ N O 3 ] a q
(3)
or igDTh = igKex*
According mol/17;
to gq.
was e v a l u a t e d consisted
of
[TBSA]
3), the v a l u e
to be 0.081
The suggested
+ ig[TBSA]org
(4) ([HNO 3] = 3.5 mol/l,
the c o n d i t i o n s
ing Kex see Fig.
4lg[NO3]aq
[NO3 ] = 3.26
and [Th 4+] for calculat-
of Kex
(50% TMB + 50% OK)
• 0.006.
structure
of Th 4+ , NO
of the 1:4:1
complex
and T B S A can be e x p r e s s e d
lows: ,,-•
~ 4~. c.-"
(4)
" ~ , c . "~
%o o// .0-. ~ / . . - 0 - .
o -.~o.;Z