Mathematical Model for 18O Separation Column
Based on Chemical Exchange Between Nitric
Oxides and Nitric Acid Solution, Operated at
Total Reflux
Mihai Secara, Diana Monica Sas
Technical University of Cluj-Napoca, Department of Automation, George Baritiu Street, No.26-28,
Cluj-Napoca, Romania
E-mails: secara_mihai@yahoo.com, sasdia@yahoo.com
AbstractThe mathematical modeling for 18O separation
column by isotopic exchange between nitric oxides-nitric acid
system is presented.
18O,
Index Termsisotopic exchange, modeling, separation
column, total reflux.
I. INTRODUCTION
I T is well known that isotopes are species of a chemical
element with the same number of electrons around the
nucleus but with different number of neutrons. The
compounds based on distinct isotopes exhibit difference in the
physical and/or chemical properties. The isotopes discovery is
based on this differences of properties.
The stable isotopes with various applications have a very
small natural abundance, compared with the predominant
isotope. For instance the natural Oxygen has three isotopes:
16
O with a concentration of 99.759%, 17O with 0.037% and
18
O with 0.204%. The possibility of any application of a
certain isotope asks its concentration compared with the
natural state. Appears the necessity to conceive and to build
dedicated equipment, based on new and new methods, able to
separate a particular isotope. On the other side is necessary a
sophisticated equipment to detect and to measure the
concentration of some kind of isotopes.
The present paper deals with the problem of the separation
equipment for the stable isotope 18O, with multiple domains of
application. The particular equipment is a separation column
and the process of isotope separation is based on chemical
exchange between nitric oxides and a solution of nitric acid.
Based of the fundamental equations which describe the
operation mode of the isotope separation process it is proposed
a mathematical model, useful for column supervision and/or
control.
It is to mention that a separation column may be operated
by total reflux when the concentration of 18O rises and no
final product is extracted.
II. MATHEMATICAL MODEL OF THE 18O SEPARATION COLUMN
BASED ON CHEMICAL EXCHANGE BETWEEN NITRIC OXIDES AND
A SOLUTION OF NITRIC ACID
A mathematical model is a set of equations able to express
in a truthful and accurate mode, the operation of any particular
equipment. The mathematical model for the separation column
was proposed by S.I. Babkov and coworkers. Later E. Monse
,Pratt,London,Cohen andW. Spindel, G. Pompidor[1-5] and J.
Nielsen [6] used and tested this model for the separation of
15
N based on isotope exchange between nitric oxides and nitric
acid. Using the same isotopic exchange between the same
compounds, in this paper is developed a mathematical model
for the separation of 18O.
In order to obtain a relative simple and still accurate model,
some hypotheses are accepted.
The elementary separation factor [1-3] has the
same value in any point of the column.
The oxygen contents in the gaseous phase is
negligible compared to the concentration in the liquid
phase.
The chemical concentration of the materials flowing
trough the column in countercurrent do not change
with the column height.
The hold-up H0 of the Oxygen has the same value on
each column plate.
 The proximity degree to the steady state, expressed 0 1 0

=
by the relative concentrations is the same in any 0 1 0
1 (7)
poin of the column. results:
Here is the isotope concentration in the liquid phase on the 0
= = 1
plate k of the column.

1 0 1
For small concentrations 1 results that so (8)
1
that From these equations it is possible to obtain the equation of
1 0 0 0 the sum dM:
= =
1 0
0
0 =
(1)
Where x0 is the 18O isotope concentration in the column = ( 0 + 0 ) 1 = 1 1
feeding material, x1 and xp are the isotope concentration in the =1
first plate, respectively in the plate from the column head (9)
(enrichment head), that is in the plate with the highest position where the factor U1 is given by the equation:
in the column. The values ; 1 ;

represent the isotope
=
concentration obtained in the steady state on the plates 1, k
and p. 1 = 0 + 0
From the equation of the elementary separation factor: =1
(10)
For small concentration, the factor U1 may by computed
1 explicitly, directly.
= If the column feed flow rate in the nitric oxides have natural
( 18)
concentration of 18O equal to 0.204% 18O, results:
1 ( 18 )
(2) 1 ( 1) and 1 = 0
result the equation of the concentration of the isotope 18O in
the gaseous phase on the plate k: so that the equation (4) becomes:
=
( 18 ) = 1
( 1) (0 ) = ( + 0 ) 1 = 1 1
(3)
=1
This equation is also valid for the transient state.[6]
The balance equation for 18O, based on the figure 1 is:
(11)
1 or
0 =
1 ( 1) 1
[log(0 )] =
= 0 1 + + 0 + 0 + + 0 1
(12)
(4)
If the column is operated at total reflux, the quantity:
For the initial condition xi = x0 and t = 0 results:
1
0 = 0
1 ( 1) 1 = 0 [ ( 1) ( )]
(5) 1
represents the mass of the 18O present in column in the time- (13)
unity, known as production by total reflux which is of Using the equation (1) results the equation:
course an improper notion.[6]
The mass of 18O accumulated in the column is given by the 1 1 0
= 1 + ( 1)
sum: 0 0 0
(14)

= 0 1 + + 0 + + 0 + 0 by replacing 1 = 0 and = there is the final result for
0
(6)
the enrichment factor:
where V0 is the mass of the Oxygen with the concentration xp
in the separation equipment but not proper in the column.
If all the column plates have the same proximity degree to 1 = ( 1) [1 exp( )]

the steady state, from the equation: (15)
 = 0

1
=
1
=

1 = 0 + 0 =
=1

1 2 1 1 1
= 0 ( + + + + + )
1 1 1 1
1
+ 0
1

0 1
1 = ( + 2 + + + + ) + 0
1 1

(17)

Because

1 +1
1 + + 2 + + =
1
(18)
for < 1 results:

1 0
1 = [( 1) ( + 0 ) 0 ]
1 1
(19)
and the time constant T is:

0
= [( 1) ( + 0 ) 0 ]
( 1) 1
(20)
As expected, for t = 0, from the equation (15) result:

= 1 =
0

meaning that no enrichment was possible.

For t = results the isotope enrichment

Fig. 1 The flow rates and concentrations for the separation column at total achieved in the steady state.
reflux

where

1
=

(16)
is the time constant necessary to put the column in the
operation mode, by total reflux.
Using the previous approximations for small concentrations
results:
III. CONCLUSION
The paper presents a preliminary stage and, therefore, an
introduction into the modeling problems for the study of
isotopic separation columns.
The column is operated at total reflux, and the isotope
enrichment = there is the final result for the enrichment
0 Inc., New York, 1951.
factor; T is the time constant necessary to put the column in
the operation mode, by total reflux.
These theoretical preliminaries will be used in deepened
studies for the physical and chemical processes in the
separation columns.
ACKNOWLEDGEMENT: This paper is supported by the
Sectoral Operational Programme Human Resources
Development POSDRU/159/1.5/S/137516 financed from the
European Social Fund and by the Romanian Government.
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