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Karanam L. Ramakumar
India
(This lecture notes was initially meant for the participants of Workshop on
“Radiochemistry and Application of radioisotopes” regularly organized by Indian
Association of Nuclear Chemists and Allied Scientists (IANCAS), a non-profit
organization based in Mumbai, India. Major portions of this document were
included in the IANCAS lecture notes brought out in 1992 and subsequently in a
book “Principles of Radiochemistry” published by IANCAS in 1993-94. This enlarged
document is uploaded for interested readers. Some figures were downloaded from
Internet.)
Introduction
Although the isotopes of an element have very similar chemical properties, they behave
as completely different substances in nuclear reactions. In addition, many of the stable
isotopes find wide spread applications in chemical, industrial, agricultural and clinical research
to elucidate and understand reaction pathways, mechanisms and kinetics, effect of trace
elements on physico-chemical properties, up-take and plant metabolism studies and the
behaviour of trace elements from toxicological and human metabolism point of view
respectively. Table 1 lists separated isotopes that are being produced on a significant
industrial scale for various applications.
In addition to these, separated isotopes of practically all natural elements are being
produced for applications in research. Very small differences that are manifested in the
Physico-chemical properties of isotopes of element, because of different masses, such as the
boiling points, diffusion coefficients, rate of electrolysis, and difference in optical properties are
exploited to achieve their separation. Almost all the methods used for separation in
conventional industries can be used for separation of isotopes also with varying degree of
success. The methods can be broadly classified into physical and chemical methods.
Physical methods are those in which difference in physical properties e.g. inertia,
density, electrical properties etc.
Chemical methods are those in which difference in chemical properties e.g. chemical
potential is harnessed
Table 2 lists some of the processes used to separate isotopes.
Method Applied to
235
Electromagnetic U, all others
Electrolysis D, Li
Distillation D, 10B, 13C, 15N, 18O
Chemical exchange D, Li, 10B, 13C, 15N, 18O
Ion migration Li
235
Gaseous diffusion U
18
Thermal diffusion O, 15N, inert gas isotopes
235
Gas centrifuge U
235
Aerodynamic U
235
Photochemical U, other isotopes
Ion exchange Lighter isotopes, 235U
Chemical methods are more suitable for light isotopes and are extensively used for
separation of hydrogen isotopes e.g. production of heavy water. Physical methods are in
general more suitable for separation of heavy isotopes e.g. uranium enrichment.
A value of α close to unity indicates that the separation is difficult, a value far from
unity, easier. For gaseous diffusion of UF6 for example, α is so close to unity (I.00429) that
the processes must be repeated many times for useful degree of separation. This is achieved
by employing stages and cascades.
Waste
Waste
Product
Counter current or recycle cascade: a cascade in which the feed for each stage consists of
heads from the next lower stage and wastes from the next higher stage is called a counter
current or recycle cascade. This is by far the most commonly employed cascade type. In
general as (α-l) < < < 1, in most of the cases, these are also known as close-separation
cascades. A recycling cascade has two sections: the enriching section, consisting of the stages
above the point at which the feed enters the cascade and the stripping section below the feed
point. The stripping section increases the recovery of the material, whereas the enriching
section produces material of increased concentration. In a symmetric counter-current cascade,
the waste stream is recycled back to the immediately preceding stage. In an asymmetric
counter-current cascade, the waste is recycled more than one stage back. A common
asymmetric cascade feeds the product stream into the next stage and sends the tails stream
back two stages back. This is called a two-up, one-down cascade. Asymmetric cascades were
used in aerodynamic nozzle separation processes. While asymmetric cascades are rarely used
for gas centrifuges, some argue that an asymmetric cascade can increase centrifuge cascade
performance by about ten percent relative to a symmetric arrangement.
Feed
Waste
Product
Fig.2 An example of tapered counter-current symmetric cascade
Feed Waste
Product
A square cascade has the same flow rates in all stages and therefore the same number
of machines per stage. Square cascades are rarely used because they are not very efficient;
constant flow rate results in constant cut and mixing of concentrations and therefore loss of
separative work.
The overall performance characteristics of enrichment plant are expressed in terms of
two factors: Separation capacity and separative work. The separation capacity is a measure of
the rate at which the cascade performs separation. In many isotope separation plants the
initial cost of plant is proportional to the separative capacity the plant. Separative capacity has
the dimensions of the flow rate (Kg of material/day). It is also useful to have a measure of the
amount of separation performed by a cascade. This measure is provided by the separative
work units (SWU). In an enrichment plant, the annual operating costs are proportional to the
amount of separative work done per year. Separative work unit, S has the dimensions of the
235
amount of material E. More number of SWUs is required to produce 1 Kg. of 90% UF6 as
235
compared to 1 Kg. of 3% UF6. Accordingly cost of enriched uranium increases with the total
235
number of SWUs and enrichment value. As an example, to get 1 Kg of 90 % enriched UF6
235
we need 178 Kg of natural uranium in UF6 feed. To get 1Kg of 3% enriched UF6 we need 5.6
Kg of natural uranium in UF6 feed.
Concept of Separative Power, Separative capacity and Separative Work Unit
It should be noted that SWUs required for enrichment increase with decreasing levels
of desired isotope in the waste streams. But the amount of feed material needed will decrease
with decreasing levels of the desired isotope in the waste streams. Thus they operate in the
opposite direction. For example in uranium enrichment we have the following expressions:
For material balance:
Total U = F = P + W (F = Feed, P = Product, W = Waste all in Kgs)
U-235 = F.xf = P.xp + W.xw (x is atom fraction of U-235)
xp −xw xp −xf
F = P W = P
xf − xw xf −xw
WSWU xp W xw F xf
= (2xp -1)ln + (2x w -1)ln - (2x f -1)ln
P 1-xp P 1-xw P 1-xf
Let us calculate the amount of feed (F in kg) required to produce 1 kg of product and the
number of SWUs needed for this operation in two cases:
It is seen that feed and SWUs operate in opposite direction. If the availability of feed is
no problem, one can save on energy consumption by allowing larger fraction of desired isotope
in the waste streams.
Various methods are employed for the separation of stable isotopes. Among these,
gaseous diffusion, gas centrifuge, aerodynamic methods, distillation, electrolysis and chemical
exchange methods, electromagnetic separation, thermal diffusion, laser methods of separation
and ion migration are described in this chapter.
Feed Product
Diffusion barrier materials should have pore sizes between 0.01-0.05 µm. They should
be chemically inert towards the operating gas. One way in which such barriers could be made
is by etching a thin sheet of silver-zinc alloy with HCl acid. The acid would then dissolve out
zinc atoms leaving a large number of pores in the sheet of metal. Other materials like sintered
alumina, nickel, anodically oxidised aluminium, teflon powder pressed into nickel gauge etc.
can also be used.
(M -M )ω2a2 r2
α= exp 2 1 (1- 2 )
2RT a
where M1 and M2 are the masses of the lighter and heavier isotopes, ω is the peripheral
velocity of the molecules, a is the radius of the centrifuge and r is the radius at any given
location in the centrifuge. R is the molar gas constant and T is the absolute temperature. The
separation factor increases with the length of the rotor, the peripheral speed and also with the
radius.
It may be seen that α depends on the difference between the masses and not on their
235 238
ratio. Thus better separation would be obtainable, in principle, of the U and U isotopes of
uranium than of the isotopes of hydrogen with masses 1 and 2. Also, since the difference in
the atomic masses is always same for a given element, the efficiency is independent of the
molecular weight of the compound whose vapour is being centrifuged. A long, thin vertical
cylinder made of material with high strength and relatively low density is used in the
construction of centrifuges. In a typical centrifuge rotating at a peripheral speed of 500 m/s,
the abundance ratio of heavier isotope to lighter isotope with mass difference = 3 at the outer
radius is greater than at the centre by a factor of 1.162 and the pressure at the outside is
greater than at the centre by a factor of 4.6 x 107. Countercurrent flow between the stream
near the outer radius and the stream near the axis is induced either with the help pf internal
scoops and baffles or by establishing a temperature gradient along the wall. This leads to
higher separating factors resulting in higher enrichment.
The main subsystems of the centrifuge are (1)
rotor and end caps; (2) top and bottom
bearing/suspension system; (3) electric motor and
power supply (frequency changer); (4) center post,
scoops and baffles; (5) vacuum system; and (6)
casing. Because of the corrosive nature of UF6, all
components that come in direct contact with UF6 must
be must be fabricated from, or lined with, corrosion-
resistant materials.
The materials used for constructing the
centrifuge should withstand tremendous centrifugal
forces resulting due to high speed revolutions of the
vertical cylinder (50000 to 100000 rpm). The
peripheral speeds reached under these conditions are
more than 500 m/s. The primary limitation on rotor
wall speed is the strength-to-weight ratio of the rotor
material. The materials therefore should have high
tensile strength, low density and high modulus of
elasticity. Further, the material should be inert to the gas being centrifuged. Aluminium alloys,
high tensile steels, titanium, glass fibres are some of the materials preferred. Another
limitation on rotor speed is the lifetime of the bearings at either end of the rotor. Rotor length
is limited by the vibrations a rotor experiences as it spins. The rotors can undergo vibrations
similar to those of a guitar string, with characteristic frequencies of vibration. Balancing of
rotors to minimize their vibrations is especially critical to avoid early failure of the bearing and
suspension systems. Because perfect balancing is not possible, the suspension system must
be capable of damping some amount of vibration.
The casing is needed both to maintain a vacuum and to contain the rapidly spinning
components in the event of a failure. If the shrapnel from a single centrifuge failure is not
contained, a “domino effect” may result and destroy adjacent centrifuges. A single casing may
enclose one or several rotors.
One of the key components of a gas centrifuge enrichment plant is the power supply
(frequency converter) for the gas centrifuge machines. The power supply must accept
alternating current (ac) input at the 50- or 60-Hz line frequency available from the electric
power grid and provide an ac output at a much higher frequency (typically 600 Hz or more).
The high-frequency output from the frequency changer is fed to the high-speed gas centrifuge
drive motors (the speed of an ac motor is proportional to the frequency of the supplied
current). The centrifuge power supplies must operate at high efficiency, provide low harmonic
distortion, and provide precise control of the output frequency.
Although the separation factors obtainable from a centrifuge are large compared to
gaseous diffusion [ranging from 1.01 to over 1.10], several cascade stages are still required to
produce even LEU material. Separation factors depend on the absolute mass difference
between isotopes (not the mass ratio) and the square of the peripheral speed. Separation
factors for U-235/238 range from 1.026 for a 250 m/sec centrifuge to over 1.233 for a 600
m/sec centrifuge. The power consumption of a centrifuge plant per unit separative capacity is
less than that of a gaseous diffusion plant. For a given mass difference between the isotopes,
the stage separation factor is more than in gaseous diffusion plant. This means far fewer
stages in series would be needed with the centrifuge to arrive at a given enrichment. For
example, to get 3 % enriched uranium, 13 stages are needed as compared to about 1300
stages required in the gaseous diffusion plant. This advantage is however, partly off set by a
lower yield per stage compared to the process of gaseous diffusion. This means a large
number of centrifuges have to he operated in parallel to multiply the net yield.
With current technology, a single gas centrifuge is capable of about 5 separative work
units [SWU] annually, while advanced gas centrifuge machines can operate at a level of up to
perhaps 40 SWUs annually. About 100-120,000 SWU is required to enrich the annual fuel
loading for a typical 1000 MWe light water reactor.
Aerodynamic Process
Processes in which isotopic composition changes are produced when a flowing gas
mixture experiences large linear or centrifugal acceleration are termed aerodynamic
processes. These processes are characterised by high speed flow of gases along a stream lined
curvature. Again, like in a centrifuge, the heavier species tend to concentrate on the outer side
of the curvature. One of the important aerodynamic processes is the jet nozzle separation
process. This process has basically been developed for uranium enrichment.
In the jet nozzle process, a mixture of
about 95% H2 and 5% UF6 at a pressure of
about 1 atm. is allowed to expand through a
narrow nozzle (0.01 mm wide) in to a curved
(0.1 mm radius) wall. The high speed gas
experiences forces 160 million times the
gravitational force in the curved nozzle. The gas
stream coming out of the nozzle is divided into
lighter and heavier fractions by a very sharp
skimmer knife. The separation factor depends
on the configuration of the nozzle, type of
diluent gas and its abundance in relation to UF6, the inlet's absolute pressure and expansion
ratio of the heavy fraction. The separation factor is higher for (i) higher pressure ratios
between the inlet and outlet streams and (ii) lower expansion ratio (flow rate of the light
fraction to that of the feed). Separation factor for the dimensions given above is around 1.015
for U isotopes. About 740 stages are required to produce 3% enriched uranium. Dilution of UF6
with hydrogen has two beneficial effects: it helps to increase the speed of flow and it delays
the establishment of a hypsometric distribution of Uf6 density. This delay reduces the re-
mingling by diffusion of the isotopes of uranium already separated by the centrifugal forces.
The Electromagnetic Method
Electromagnetic separation of isotopes of elements makes use of principle underlined in
mass spectrometry. In short, whenever an ion of charge ne (n is number of charges) and
mass m (amu) is accelerated in an electric potential of V (volts), it gains kinetic energy, which
is given by
1
K.E. = mv2 = neV
2
where v is the velocity of ions. If these accelerated ions pass through a magnetic field of
strength H (Tesla), in a direction normal to the application of magnetic field, then a force
equivalent to Hev is experienced by the ions. The direction of this force is mutually
perpendicular to the direction of the ions as well as magnetic field. This force is balanced by
the centripetal force given by mv2/r. So we have
mv2
Hev =
r
Where r is the radius of the path described by ions under the influence of the magnetic field.
Eliminating velocity (v) term from equations 1 and 2, we get the well known mass
spectrometric equation
m H2r2
=
ne 2V
Thus, ions of different masses but with same kinetic energy and charge describe different radii
in the applied magnetic field and can be resolved according to their mass to charge ratio. For a
given constant magnetic field and kinetic energy,
m
α r2
ne
Electromagnetic separation of isotopes is therefore possible.
Historical Perspective
Electromagnetic separation of uranium isotopes was one of the three major processes
considered by USA under the “Manhattan Project” during World War II period. The other two
were gaseous diffusion and centrifugal separation. Of the many electromagnetic schemes
suggested, three soon were recognized as being the most promising: the “calutron” (a name
representing a contraction of “California University cyclotron”) mass separator, the
magnetron-type separator later developed into the “ionic centrifuge,” and the “isotron”
method of “bunching” a beam of ions. The first two of these approaches were followed at
California and the third at Princeton.
Calutrons are basically 1800 deflection magnetic analysers. The isotron is an
electromagnetic mass separator using extended source of ions, in contrast to the slit sources
used in ordinary mass spectrographs. The ions from the extended source are first accelerated
by a constant, high-intensity, electric field and are then further accelerated by a low-intensity
electric field varying at radio frequency and in “saw tooth” manner. The effect of the constant
electric field is to project a strong beam of ions down a tube with uniform kinetic energy and
therefore with velocities inversely proportional to the square root of the masses of ions. The
varying electric field, on the other hand, introduces small, periodic variations in ion velocity,
and has the effect of causing the ions to “bunch” at a certain distance down the tube. (This
same principle is used in the klystron high frequency oscillator, where the electrons are
“bunched” or “velocity-modulated.”). The bunches of ions of different mass travel with
different velocities and therefore become separated. Separation of isotopes using Magnetron
or ionic centrifuge was based on the fact that the strong centripetal acceleration in a rotating
plasma typically of the order 5 x 1010m/sec2, can be used for separating difference species of
elements and isotopes.
Isotope Separators
Electromagnetic separators are large-radius (e.g., 24 in.), 1800 deflection mass
spectrometers. Ions are normally obtained in low voltage (100-150 V) arc discharge sources.
The arc current is about 3-5 A, while the ion current obtained is of the order of a few hundred
mA. Ionization efficiency is usually of the order of 5%. Gaseous materials, often in the form of
chlorides SnCl4, SiCl4) are continuously fed into the arc chamber through a controlled leak.
The pressure inside the arc chamber must be kept constant to obtain a steady ion beam.
Compounds which can be volatilized in the 100-6000C-temperature range (chlorides, bromides
of many elements) are introduced through a heated stainless steel “charge bottles”.
Temperatures as high as 12000C can be obtained with graphite “charge bottles”.
The pumping systems of large separators are impressive indeed. The main requirement
is pumping capacity rather than ultimate vacuum. In a large instrument, total pumping
capacity as high as 20,000 liters/sec is employed to maintain a vacuum of 10-5 torr.
The collection of the separated isotopes presents many problems. First of all, considerable
cooling is necessary. When an ion beam of 100 mA, accelerated to 35 kV, impinges on a
metallic receiver, the heat generated is of the order of 3.5 kW.
Other problems which must be considered in the design of a collector system are
erosion, sputtering, efficiency, and technique of isotope removal. Graphite and copper are the
most frequently used collector materials. The collected material is often removed from
graphite by simple scraping or by the burning of the entire pocket in oxygen. Dissolution in
nitric acid is a frequent removal method with copper pockets. Mercury isotopes may be
collected in silver pockets from which removal is easily accomplished by heating in vacuum.
Enrichment factor and production rate are two important performance parameters in
electromagnetic separators. The enrichment factor is the ratio of the ratios of the isotopic
concentrations in the product and the starting material, i.e., A/B in the product over A/B in the
feed gas, where A is the “wanted” isotope. Enrichment factors are normally in the 30-50
range; in special applications enrichment may be as high as 1000. The production rate of the
separators greatly depends on the throughput. A current of 1 mA corresponds to 6.3 X 1015
unit charges per second. A current of 100 mA will produce about 10 g of a nuclide of mass 100
in a full day’s operation; about one-half of this amount may be recovered from the collector.
Since the efficiency of ionization, as mentioned, is below 10%, at least 100 g of charge
material is required.
When the “wanted” isotope is a rare nuclide, production rate may be very poor; for
4O
example, K can only be produced at a rate of 0.5 mg/day. In cases like this, other
separation methods such as chemical exchange, thermal diffusion, and distillation should be
used if at all possible.
Charge Materials
For charge materials occurring as liquids or gases at room temperature, sample
introduction systems external to the ion source can be employed. The flow of feed material to
the arc region should be controllable with the help of a sensitive needle valve.
In the case of Solid materials, usually they are introduced in a contained inside the ion
source and are heated. Usually it is desirable to have a small flow of gas such as nitrogen into
the arc is beneficial, and with some elements necessary, for stabilizing the arc and promoting
production. The problem of producing ions of all isotopes for calutron operation is not
completely solved; however, methods and equipment now in use are adequate to produce
ions, with varying degrees of efficiency, from virtually any element in the periodic chart.
Magnetic Analysers
A special class of shaped magnetic lenses, used successfully in beta-ray spectroscopy
have found wide spread applications in isotope separations. The fundamental concept of this
focusing system relates to the use of magnetic field that decreases in intensity with increasing
radius. The approximate magnetic field intensity distribution across the mid plane in these
“inhomogeneous systems” is given by the relationship
n
r
βr = β0 0
r
where βr is the mid plane magnetic field as a function of radius, r0 is the radius of the central
orbit, β0 is the mid plane magnetic field strength at r0 and n is the inhomogeneous filed index.
Siegbahn and Svartholm have shown that under these conditions, both radial (φr) and
azimuthal (φz) focusing occurs when φr = φz = √2n= 2550 and at this focusing angle and for n
= 0.5, spherical aberration is minimized. Both the radial and azimuthal or axial trajectories
converge to the same image point. As a result, the transmission of a 2550 analyser can
approach 100%. for reasonable ion source limits relating to angular divergence and ion energy
spread. In addition, increase in mass or energy dispersive power is realized. The increased
dispersion is extremely valuable for it permits the use of a magnet smaller than a
homogeneous type. For a magnet having a basic radius of curvature r0, with the object and
image symmetrically located, the dispersion D is given by
r0 ∆m
D=
m0 (1 − n)
where n is the index of inhomogeneity of the magnetic field. For a 0.5 index the dispersion is
doubled. Such an isotope analyser has been constructed. It had a transmission approaching
100% for several types of ion sources. The mean radius of curvature of this 75 ton
electromagnet is 6 cm, the pole-piece gap width at this radius is 10 cm, and the mass
dispersion at mass 100 is about 1.5 cm.
Isotope Collectors
For each element processed, an isotope collector must be designed, providing properly
spaced receptacles for whatever isotopes may be present. Isotope collector structural
materials, structural design, and cooling, all require considerable attention and have to be
chosen depending on the system being studied. Since one mass unit separation at the
collector decreases as the mass of the ions increase, each element requires especially
designed collectors. In addition to this consideration, which is essentially a problem in pocket
placement, suitable pocket materials and cooling techniques must be chosen in order to retain
the deposited material. The temperature of receiving surfaces, which must necessarily be
bombarded With ions, must be kept sufficiently low that deposited material Will be retained
and not lost to cooler surfaces such as walls of the vacuum chamber
through the vacuum system. The problem of building a collector for any element then consists
of calculating proper pocket spacing for the desired isotopes, and from vapor pressure
considerations, determining suitable pocket material and cooling techniques.
Usually the design of a collector is dictated by the desire for having maximum flexibility
so that collectors could be constructed for any element from a minimum number of parts. The
all-purpose type collector, in which pockets up to 10 can be assembled at predetermined
spacings has been fabricated for this purpose. This basic structure permits the placing of
collectors to receive the isotopes of any element in the periodic chart; pockets may be
replaced easily if desired, and cooling may employed as required.
Collector Materials
These vary with the element being processed, and the receiver parts may or may not
be water-cooled, depending on the energy to be dissipated and the vapor pressure of the
collected material. Furthermore, with some elements, special retention techniques are
required. For example: Sulfur is allowed to combine chemically with copper shavings packed in
the collector pocket. Mercury is retained by allowing it to amalgamate with silver collector
pockets, and by cooling the pockets with a circulating refrigerant. In the processing of
mercury, the problem of high vapor pressure in the calutron and the contamination of
collected isotopes by the condensation of neutral mercury vapor in the collector pockets,
needs to be eliminated by refrigerating the, vacuum chamber.
Thermal Diffusion
When heat flows through a mixture initially of
uniform composition, small diffusion currents are set up,
with one component transported in the direction of heat
flow, and the other in opposite direction. This is known as
thermal diffusion effect. The effect is generally small. For
example when a mixture of 50% hydrogen and 50 %
nitrogen is held in temperature gradient between 260 and
10°C the difference in composition at steady state is only
5%. In isotopic mixtures the effect is even smaller. The
mixture to be separated is confined in a long, vertical tube,
cooled externally and heated internally by a hot wire at the
axis of the tube. Concentric annular type cylinders can also
be used. In both types, the mixture to be separated is
confined in a narrow space between the inner heated and
an outer cooled surface. As a result of thermal diffusion
effect, the lighter isotope usually concentrates in the inner zone at higher temperature. At the
same time, convection currents are set up, with the lighter isotope adjacent to the inner wall
moving upward and the heavier isotope adjacent to the outer wall moving downward. Thus it
is possible to achieve substantial degrees of separation in a practical length of column. It is
preferable to work with gases rather than liquids because the higher diffusion coefficients
result in higher separative capacity. The optimum space between hot and cold surfaces is a
few mm for gases and fraction of mm for liquids. A series of very long columns (tens of
meters) are essential to achieve reasonable degree of enrichment.
Distillation methods
In general, isotopic species have different vapour pressures (and boiling points), so
that partial separation by fractional distillation can be employed for their separation. For
example, the boiling point of D2O is about 1.4° higher than that of H2O. This difference,
though small, should make separation by distillation practical, provided efficient columns are
used. Deuterium can also be separated by fractional distillation of hydrogen gas at low
temperatures (< -250°C). Heavy hydrogen gets concentrated in liquid phase.
The separation factor α, for the desired component is given as
x/(1-x)
α =
y/(1-y)
where x is the fraction of the component in the liquid phase and y is the fraction in the vapour
phase. Deuterium in hydrogen or in water is always in equilibrium according to the reactions
H2 +D2 ↔ 2HD and
H2O + D2O ↔ 2HDO
If the liquid and vapour phases form ideal solutions, the separation factor α can be written as
1/2 1/2
π(H 2 ) π(H 2 O )
α(H /D ) = α(H 2O /D 2O ) =
π (D 2
) π (D 2
O )
where π is the vapour pressure. The separation factors for H2/HD and H2O/D2O at their boiling
points are 1.81 and 1.03 respectively.
The elementary separation factor in the distillation process can be multiplied by inducing a
countercurrent flow in the distillation columns (or towers). These columns are cylindrical
containers within which contact is made between the two phases; (i) the liquid phase that
flows by gravity from top to bottom and (ii) the vapour phase that, produced in a reboiler at
the base of the column, flows from bottom to top. Distillation columns can be divided into two
basic categories; plate columns and packed columns. In the former, there is repeated contact
between the two phases, whereas the latter operates on the principle of continuous contact.
Electrolysis
During the electrolysis, the gas discharged at the cathode of an electrolytic cell is
distinctly poorer in heavier isotope content than in the electrolyte. Separation factor is defined
as
(M 1 /M 2 ) electrolyticgas
α =
(M 1 /M 2 ) electrolyte
It has been found that α depends on the cathode material, electrolyte composition and cell
temperature. In the case of water for example, a high value of 8.1 has been reported.
Separation factor is higher for an alkaline electrolyte than for acid. With KOH at 15°C, a pure
iron cathode gave the highest value of 13.2. Minimum is expected to be about 3.8 as dictated
by the equilibrium constant for the reaction
The deuterium exchange reaction between water and ammonia, water and hydrogen
sulphide proceeds rapidly in the liquid without catalysis, because of ionic dissociation. On the
other hand, deuterium exchange between water and hydrogen, ammonia and hydrogen or
methylanline and hydrogen does not proceed without catalysis. The water-hydrogen reaction
can be catalysed by nickel or platinum metal catalyst, ammonia-hydrogen reaction by
potassium amide dissolved in liquid ammonia and the methylamine-hydrogen reaction by
potassium methylamide.
Solutions used in the ammonia-water, water-hydrogen and ammonia-hydrogen
processes are relatively non-corrosive and may be handled in ordinary steel equipment.
Solutions used in all of the other processes are relatively corrosive, and require use of
stainless steel or other expensive construction materials. For example, in water-hydrogen
sulphide exchange reaction (also known as Guilder-sulphide (GS) process), H2S is highly
corrosive. Carbon steel coated with iron sulphide and bubble trap trays made of SS-304 are
used.
In all the above processes, to achieve a multiplication effect for the overall separation
factor, the light and isotopic fractions collecting at the two ends of the column are reconverted
to the initial chemical forms and returned to the exchange column to recycle countercurrently.
To illustrate, consider the equilibrium reaction H2O(l)+HD(g) <==> HDO(l)+H2(g), The
hydrogen gas, depleted in deuterium, escaping at the top is burnt with oxygen and the water
formed flows back down the column again while the water, enriched in deuterium, collecting at
the bottom is electrolysed into hydrogen and the gas is made to re-ascend the exchange
column for further exchange with water flowing down.
Alternately, a dual temperature exchange or bi-thermal exchange process can be set
up to avoid the cumbersome exercise of
Feed: Recycle D2S
reconverting the products into initial
Natural water Blower reactants to achieve the multiplication
effect in the separation factor. The dual
Cold tower
T = 320C temperature exchange takes the
α = 2.32 temperature dependent property of the
equilibrium constant for the exchange
D2S flow reaction under consideration. For
Depleted water
example, the values for the K for the
Product D2O flow
reaction
Heat H2O(l) + HD(g) < = = > HDO(I) + H2(g)
exchangers
Ion Migration
Slight differences in velocities of isotopic ions in solution under an electric field, can
also be exploited for the separation of isotopes. These small differences are due to the
different sizes and masses of the ions. Contributions due to differences in the degree of
dissociation and in complex formation have also to be taken into consideration. The ion
migration can occur not only in aqueous media where the ions are invariably hydrated but also
in fused salt media where the ions are relatively more free from solvation effects. The major
advantage of the fused salt medium is the absence of ion solvation resulting in larger mass
effects in the migration of isotopic ions. The separation factor in ion migration process is
proportional to ∆v/v where ∆v is difference in velocities between the isotopes and v is the
mean velocity. The extent of separation effect between the two isotopes can also be expressed
in terms of relative mass effect given as
∆v / v
-µ =
∆m / m
where m is the mass of the ion. Thus the actual enrichment factor is somewhat less than
expected when only velocities are considered. More over, while electromigration builds up a
concentration gradient along the field direction, the reverse flow of the electrolyte due to
39 41
diffusion tends to neutralise the effect partially. In a typical example, K and K were
separated by the electromigration of potassium chloride solution in a U-shaped tube using
platinum gauge electrodes, with an arrangement for controlled counter flow of HCl acid from a
reservoir above the cathode compartment. The tube was packed with glass beads or sand held
under pressure. The counterflows were so adjusted that the speed of H+ ions was intermediate
39
between those of K+ and 41
K+ ions. 41
K+ ions were washed back while the faster moving 39
K+
ions moved ahead thereby building an isotopic concentration.
Baroda
Heavy Water Plant at Baroda is the first plant set up in the country for the
production of heavy water by employing Monothermal Ammonia-Hydrogen
exchange process. This facility also has a Potassium metal plant for supply of
Potassium metal for preparing catalyst solution for all Monothermal
Ammonia-Hydrogen exchange plants. In 1999, M/S GSFC commissioned their
new technology based low-pressure Ammonia plant (A4), operating at around
140 kg/cm² pressure, and stopped operation of their old high pressure
(640kg/cm²) ammonia plants. Operation of HWP had to be suspended
simultaneously due to non-availability of synthesis gas at high pressure.
Facing the challenge, HWP is modified to reorient its operation independent of
GSFC. The Ammonia Water Exchange Front-End unit is set up which
eliminates dependency of HWP on Ammonia plants of M/S GSFC for its
deuterium feed stock. It uses water as the source of deuterium in the process
and ammonia works as carrier gas only.
Hazira
Heavy Water Plant at Hazira, employs the ammonia-hydrogen exchange
monothermal process. The plant is located at a distance of about 16 km from
Surat city. Work on HWP (Hazira) commenced in August 1986 and the plant
was commissioned in February 1991.
Thal
The plant comprises of two streams consisting of two separate isotopic
exchange units, final enrichment units, final production units & cracker units,
but a common ammonia synthesis unit. Feed synthesis gas (a mixture of one
part of nitrogen and three parts of hydrogen containing deuterium from the
Ammonia plant is routed through the plant at a flow rate of about 96 T/Hr. at
a pressure of about 180 kg/cm². The deuterium enriched ammonia from the
bottom of the exchange tower is then fed to the second isotopic exchange
tower where it gets further enriched by coming in contact with the enriched
synthesis gases obtained by cracking of enriched ammonia. A part of the
enriched gas and liquid from the second isotopic exchange tower is then
taken to the final enrichment section where the concentration of deuterium in
the ammonia can be further increased as desired upto 99.8%. Finally, the
enriched ammonia so obtained is made free of the catalyst and is cracked. A
portion of this enriched synthesis gas is burnt to produce heavy water.
However, for reasons of better recovery efficiency the concentration of
deuterium in ammonia in the final enrichment section is kept low so as to
produce heavy water of about 60% which is then vacuum distilled to produce
heavy water of nuclear grade.
Manuguru
The Heavy Water Plant at Manuguru, Andhra Pradesh is based on the
Bithermal Hydrogen Sulphide-Water (H2S-H20) Exchange Process. This plant
with a capacity of 185 MTY is the second plant based on this process, the
earlier one being at Kota, Rajasthan for which the complete technology has
been developed indigenously by BARC and HWB. Water from the nearby
Godavari river, purified from both suspended and dissolved impurities forms
the process feed and the D20 content is enriched from 150 ppm (0.015%) to
15% D20 by chemical exchange with H2S and later vacuum distilled to
produce 99.8% D20.
SUGGESTED READING
1. K. Cohen, The theory of isotope separation, Mc Graw Hill, New York (1951)
2. M. Benedict and T.H. Pigford, Nuclear chemical engineering, Mc Graw Hill, New York
(1965)
3. H. London, Separation of isotopes, George Newnes, London (1961)
4. S. Villani, Isotope separation, Amer. Nucl. Soc., Hinsdale, (1976)
5. H.J. Arnikar, Isotopes in atomic age, Wiley Eastern, New Delhi, (1989)
6. J. Koch(Ed.), Electromagnetic isotope separators and applications of magnetically
enriched isotopes, Interscience, New York (1958)
7. G.M. Murphy(Ed.), Production of heavy water, Mc Graw Hill, New York (1955)
QUESTIONS
1. Mention two important and widely used methods each for the separation of uranium
isotopes and hydrogen isotopes.
2. Bring out clearly the difference between the separation factor and enrichment factor.
3. Mention the physico-chemical property on which the following methods for separation
of isotopes are based: (a) gaseous diffusion (b) distillation (c) thermal diffusion (d)
chemical exchange
4. Define the terms separating unit, stage and cascade.
5. Why do we need to employ series of stages and cascades in the separation of isotopes?
6. Name some of the important applications of stable isotopes?
7. Better separation of uranium isotopes is possible in principle with gas centrifuge
methods than with gaseous diffusion methods. Why?
8. Why is UF6 diluted with hydrogen in jet nozzle process?
9. Can one employ distillation methods for the separation of uranium isotopes? Justify
your answer.
10. Explain briefly the Guilder-Sulphide (GS) process in the separation of hydrogen
isotopes?
11. For deuterium enrichment, chemical exchange methods are preferred to distillation
methods. Why?
12. What is the difference between squared-off cascade and tapered cascade? Give an
example of each.
13. Which type of the cascade is preferred for obtaining high recovery of the product:
Simple cascade or counter current cascade? Justify your answer.
14. Calculate the number of stages required to get enrichment of U-235 from its natural
value of 0.77 % to 3% employing gaseous diffusion method.
15. Can a mass spectrometer be used for the separation of isotopes? Justify your answer.
16. What are the limiting factors deciding the maximum enrichment possible in laser
isotope separation of isotopes, even though very large separation factors are possible?