Methods for the separation of stable

isotopes

Karanam L. Ramakumar
India

Karanam L. Ramakumar 1
 Isotopes of an element have very similar
chemical properties
e.g. 235U O and 238U O Chemical
3 8 3 8
reactivity is nearly identical

They behave as completely different

substances in nuclear reactions
e.g. 235U is a fissile isotope while 238U is
not

Karanam L. Ramakumar 2
 Many of the stable isotopes find wide spread
applications in chemical, industrial,
agricultural and clinical research

Elucidate and understand reaction pathways

Mechanisms and kinetics

Effect of trace elements on physico-chemical
properties

Up-take and plant metabolism studies

Behaviour of trace elements from
toxicological and human metabolism point of
view

Karanam L. Ramakumar 3
 Mass differences result in
Thermodynamic isotopic effects
Shift in equilibrium in reactions
Kinetic isotopic effects
Shift in rate of reactions
Isotopic effects are quite pronounced in light
elements
Negligible in heavy elements

“The reasonable man adapts himself to the world,

the unreasonable man persists in trying to adapt
the world to himself. Therefore all progress
depends on the unreasonable man”
George Bernard Shaw
‘The Revolutionist’s Handbook’

Karanam L. Ramakumar 4
 Separation Factor in a Typical Enrichment Process

Two types of separation factor

Feed Product
(i) separation factor (α
α) and
z, (1-z) y, (1-y)
α= y/(1-y)
z/(1-z)
Tails
(ii) enrichment factor (ε) x, (1-x)
ε= y/(1-y)
x/(1-x)
z is the atom % abundance of the desired isotope in the
feed. (1-z) is the corresponding quantity of the other
isotope in the feed
y and (1-y) refer to the corresponding quantities in the
product and
x and (1-x) are defined for tails

Karanam L. Ramakumar 5
 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) 
x -x  
x -x 
   
F=P  xp-x w  W=P  x p-x f 
The ratio of products  f w  f w
   

flow rate to feed flow

rate is called “cut” θ Fraction of desired
 component in products
xF-xw 
θ= Product flow rate = P

θ= x -x 
 stream is called recovery
Feed flow rate F 

P w “r”
 

1 - θ = W/F r = yzθ = 1 − x(1z−θ)

Cut (θ
θ ) for a given enrichment cascade is
optimised
Karanam L. Ramakumar 6
 Separating Unit, Stage and Cascade

Separating Unit: The smallest element of an isotope

separation plant that effects some separation of the
process material
Examples of a single separating unit are one gas
centrifuge, or one electrolytic cell etc.
No single separating unit can enrich any material to
desired value. Throughput is also very very small
To multiply the effects of the enrichment of one
unit and to achieve adequate throughput large
numbers of units are interconnected in parallel
Stage: A group of parallel-connected separating units, all
fed with material of same composition and producing
partially separated product streams of the same
composition
Cascade: A series-connected group or stages
Karanam L. Ramakumar 7
 Cascade
Stage
y1

x1 y2

Z1 y1 x2 y3
Unit
Feed
x1 y2 x3

y1 x2

x1

Concept of Unit, Stage and cascade

Karanam L. Ramakumar 8
 Square Cascade A square cascade has
the same flow rates in
Feed
Waste all stages and
therefore the same
number of machines
per stage.
Rarely used because
they are not very
efficient.
Constant flow rate
results in constant cut
and mixing of
concentrations and
therefore loss of
Product
separative work.

Karanam L. Ramakumar 9
 Simple cascade No attempt is made to
reprocess the partially
Feed
Waste depleted waste streams
leaving each stage.
it is impossible to obtain
high recovery of desired
Waste
component because of
losses in the waste
streams leaving every
stage, the recovery falls
Waste rapidly as the over all
enrichment factor
desired is increasing.
Product
A simple cascade has
only enrichment section.
Karanam L. Ramakumar 10
 Counter current or recycle cascade

As (α-l) < < < 1, in most of Feed for each stage consists of heads
the cases, these are also from the next lower stage and wastes
known as close-separation from the next higher stage
cascades. The most commonly employed cascade
Feed
Waste
Two sections: the enriching section,
consisting of the stages above the
point at which the feed enters the
cascade and produces material of
increased concentration.
The stripping section is below the feed
point and increases the recovery of the
material

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
Product more than one stage back.
Karanam L. Ramakumar 11
 Separation of heavy isotopes
e.g. 235U from 238U

Karanam L. Ramakumar 12
 Concept of Separative Power, Separative capacity and
Separative Work Unit

In conventional industries, where the level of separation

is almost 100%, throughput parameter is sufficient to
indicate the capacity of the separating plant
e.g. a heavy water production plant, where the
grade is fixed for reactor use.
Petroleum refineries
In the case of uranium enrichment, two parameters
namely extent of enrichment and total quantity of
enriched isotope decide the plant’s capacity
e.g. 3% for LWRs to 90% & above for weapon
grade
To compare the capacities of two different plants, only
throughput may not be sufficient to gauge the size of an
enrichment plant, particularly when enrichment levels at
which the plants are operating are different
Karanam L. Ramakumar 13
 Separative power or Separative capacity
A combined function of quality & quantity of separation
performed by a separating element or a plant
It is independent of the level of concentration of feed
material
Separative power: A change in the Value effected by a
separating element, i.e. the increase in the value of output
over the value of input.
A quantity called value function is defined as a function of
the concentration, x, of the desired isotope by the
 
relation:  x 
V(x)=(2x-1)ln 
1-x 

 

The work WSWU (separative work per unit time) necessary

to separate a mass F of feed of assay xf into a mass P of
product assay xp, and tails of mass T and assay xt:

W = P.V(xp) + T.V(xt)-F.V(x )
SWU f
Karanam L. Ramakumar 14
 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-x  

F=P x -x  

W=P x -x f 


w  f w  f
   


xF-xw 
 
xP-xF 
Cut θ= x -x 



(1-θ) = x -x 

P w  

P w
 

     
xp    x   x 
WSWU =P(2xp-1)ln w f
 +W(2xw-1)ln 
   -F(2x -1)ln 
 f  
1-xp   1-xw 

1-x 
     f 

     
WSWU  xp  x x
W(2x -1)ln w  - F(2x -1)ln f 
  
=(2xp-1)ln +
w
P 
1-xp  P 1-x  P
w
f 1-x 
 f
     

Karanam L. Ramakumar 15
 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:

Case # F(kg) SWU

Case 1: Xf = 0.00711,
Xp = 0.9, Xw = 0.002
176 229
Case 2: Xf = 0.00711,
Xp = 0.9, Xw = 0.003
218 193

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.

Karanam L. Ramakumar 16
 Gaseous Diffusion Process

The gaseous diffusion process makes use of the

phenomenon of molecular effusion to effect separation.
If a gas is allowed to pass through a porous membrane
with pore sizes equal to the at molecular dimensions, the
relative frequency with which molecules of different
species pass through the pores is inversely proportional
to the square root of their molecular weights. For a
mixture of two masses M1 and M2 (MI < M2), this ratio,
called separation factor, α, is given by

α=[M /M ]1/2
2 1
Karanam L. Ramakumar 17
 Gaseous diffusion process
Feed Product
z, M1, p1 y
1-z, M2, p2 (1-y)
Porous membrane

Rate of diffusion (D) α 1 1

Density (D) α Mass

No. of molecules crossing the barrier α pressure x diffusion rate

J α P.D (p α z)
1 1
y = J1 α . z. 1 /2 (1-y) =J2 α (1-z) 1 /2
M1 M2
y = z M2
M2
α=
1−y 1−z M M1
1
Karanam L. Ramakumar 18
 Separation of U-235 from U-238 by gaseous diffusion
Feed : UF6 M1 = 235UF6 = 349 M2 = 238UF6 = 352
  M  
Separation factor  y /(1 − y)  α 2  352  = 1.00429
   
 z /(1 − z)  M1  349 
  

Separation factor is very close to 1!!

Back-diffusion brings it down further.
For useful degree of enrichment, many stages in series
(Cascade) are employed.
Lower elements have better separation factor
20Ne-22Ne = 1.0488 36Ar-40Ar = 1.0541 D-H2 = 1.414

Karanam L. Ramakumar 19
 Natural uranium U-235 : 0.00711%
Product U-235 : 0.03%  
 x (1 − x )
Tails U-235 : 0.002% n = 2 ln p w 
α−1  xw(1 − xp)
No. of stages required (n): 1275  

UF6 is highly reactive, powerful fluorinating reagent

B.Pt. = 56.40C Vapour pressure at 250C = 111.9 mm
(Hg)
Gaseous diffusion of UF6 : a technological challenge
Materials compatible with UF6
Lubricants Complete elimination of air
Seals and gaskets leakage inside the process
Diffusion cells system!!
Diffusion membranes
Compressor materials
Karanam L. Ramakumar 20
 Materials used in diffusion plants
Fluorocarbons and chlorocarbons as lubricants and
gasket valves
Alumina or Nickel vessel protected by chemisorbed
Nickel fluoride layer
Alumina or Aluminium protected by alumina for
construction of plant
Diffusion membrane : Chemically resistant, even sized
and shaped pores of radius ≤ 10 nm
Large porosity : 109 / cm2
Small thickness and sufficient mechanical strength
Diffusion membrane is Key to the process
Method of manufacture and performance characteristics
remain classified

Karanam L. Ramakumar 21
 Diffusion membrane materials
Metals : Au, Ag, Ni, Al, Cu
Oxides : Al2O3
Fluorides : CaF2
Fluorocarbons : Teflon
Film type membranes : Pores are bored through
an initially non-porous membrane
Alloy of Ag(66) + Zn(34) HCl leaching of Zn
Au(40) + Ag(60) HNO3 leaching of Ag
Al sheet anodically oxidised by 5% H2SO4
Aggregate type membranes : Pores are the voids
left when fine particles are agglomerated under
pressure or sintered at convenient temperature
Sintered Al or Ni powders
Teflon granules pored into a grid
Karanam L. Ramakumar 22
 Product
Wt. Fr. U-235 = 0.03 Stage 1275

~ ~
~ ~

Stage 594 ~
~ ~
~ 0.007125
Natural U A
feed
0.007095
Control
Wt.Fr. U-235 ~ Cooler valve ~
=0.00711 ~ Compressor ~
Stage 1

Tails
Wt.Fr. U-235 = 0.002

Ideal Gas Diffusion Cascade

Karanam L. Ramakumar 23
 Centrifugal Methods
 
(M2-M1)ω2a2
 
(1-r 2 )
2
Separation factor α α=exp 


2RT a 
 

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
r is the radius at any given location in the centrifuge
R is the molar gas constant
T is the absolute temperature
α increases with the length of the rotor, the peripheral speed
and also with the radius.
α depends on the difference between the masses
Better separation possible, of the 235U and 238U isotopes of
uranium than of the isotopes of hydrogen with masses 1 and 2
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

Karanam L. Ramakumar 24
 When a gas or vapour flows into a
rapidly rotating centrifuge, the force
acting on the molecules will produce an
increased concentration of the heavier
isotope at the walls, while the lighter
isotope tends to collect nearer the axis
of rotation. If the centrifuge is vertical,
a current of vapour can be made to
flow down near the axis and up near
the wall. It should then be possible to
draw off a product richer in the lighter
isotope at the bottom of the apparatus,
near the centre, whereas the heavier
species would be removed at the top
near the periphery. The separation
factor α for centrifugal method along
the radius is given by
 
(M2-M1)ω2a2
 r2 
α =exp  (1- )


2RT a2 
 
Karanam L. Ramakumar 25
 Pressure gradient of the gas
Ph = P0 exp (-Mgh/RT)
For two masses M1 and M2 (M1 < M2) Separation factor
depends on mass

 P1   P1  difference
  =  exp[−(M1 − M2)gh/RT]


P2   P2 
 
 h  o Separation factor
same for same
mass difference
Pressure gradient between the axis and the wall (light and heavy
Pa <<<<< Pw elements!!)

Lighter isotope accumulates near the axis

Heavier isotope accumulates near the wall

Karanam L. Ramakumar 26
 For a given mass difference between the isotopes, the
stage separation factor is more than in gaseous diffusion
plant.
To get 3 % enriched uranium, 13 stages are needed in
centrifuge as compared to about 1300 stages required in
the gaseous diffusion plant.
This advantage is partly off set by a lower yield per
stage compared to the process of gaseous diffusion.
Large number of centrifuges need 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 120,000 SWU is
required to enrich the annual fuel loading for a
typical 1000 MWe light water reactor.
Karanam L. Ramakumar 27
 Separation factor does depend on the angular velocity (peripheral
speed of the rotor)
Peripheral speed Separation factor Pressure ratio between axis
m/s and wall
400 1.0975 5.5 x 104
500 1.156 2.5 x 107
600 1.233 4.5 x 1010
700 1.329 3.3 x 1014

Maximum velocity is limited by tensile strength of the rotor T.S. >

ρω2r2
Aluminium alloys
Titanium alloys
High tensile steels
Polyamides
Karanam L. Ramakumar 28
 Advantages of gas centrifuge over gas diffusion
processes of enrichment

Higher separation factor hence requires less number of

stages.

Absence of inter-stage gas compressors in centrifuge

plant allows it to be squared off more towards ideality.
Whereas in case of gas diffusion plant use of
compressors makes it necessary to go for bigger
squaring off (more off from ideality) in order to avoid
use of large number of compressors of different
capacities. This makes the centrifuge cascades more
efficient.

Gas centrifuge being modular in construction, capacity

addition can be done more easily. The plant can initially
be constructed for lower capacity and can subsequently
be expanded without much penalty.

Karanam L. Ramakumar 29
 Gas diffusion plants must be of large capacity to be
economical due to requirement of large number of supporting
systems like captive power plants etc. Whereas the gas
centrifuge plants can be economical in smaller capacities.
Higher material inventory in gas diffusion plant makes it more
difficult to switch over from one level of enrichment to
another in an operating plant without a sufficient lead-time.
This reduces flexibility of the plant in catering to different
users requiring different enrichment levels in short delivery
periods. In G.C. plants this problem does not arise due to
much lower material inventories.
It has low equilibrium time, which reduces time between start
up of the plant and start of withdrawal of product. Gas
centrifuge process is considered superior above nozzle
process also because of low separation factor (compared to
gas centrifuge) and very high-energy consumption of nozzle
process.
Karanam L. Ramakumar 30
 Aerodynamic methods Nozzle separation process

Processes in which isotopic composition changes are

produced when a flowing gas mixture experiences large
linear or centrifugal acceleration are termed
aerodynamic processes.
Product

Feed Tails

S = 0.03 mm
A = 0.1 mm
95% H2 + 5% UF6 feed
α = 1.01 to 1.05

Karanam L. Ramakumar 31
 Jet nozzle process

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.
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.
About 740 stages are required to produce 3% enriched
uranium.
Karanam L. Ramakumar 32
 Aerodynamic methods Nozzle separation process

Dilution of UF6 with hydrogen has two beneficial

effects:

It helps to increase the speed of flow

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.

Karanam L. Ramakumar 33
 Thermal diffusion
When heat flows through a
methods 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.
Karanam L. Ramakumar 34
 Thermal diffusion methods
Separation of molecules of
different masses by radial
SS
diffusion in cylindrical columns
due to temperature gradient Cu
across cylinder walls
Vertical separation due to Ni
temperature-induced
convection currents
One of the methods first
adopted in Manhattan project
Uranium was enriched to about
15 meters height
1% which was taken to
Inner tube (Ni) at 2860C
electromagnetic separation for
Outer tube (SS) at 640C
further enrichment Gap between Ni and Cu tubes ~
Solutions can also be enriched 1mm
Separation factor ~2 Material passes through this gap
Equilibration time ~ weeks
High energy incentive!!
Karanam L. Ramakumar 35
 Electromagnetic separation methods
Mass spectrometric principle
Mono-energetic ion beams are deflected by magnetic fields to
different m/e charge ratios

M = H2r2
e 2V

Requirements
Ion source
Acceleration field
Magnetic field analyser
Suitable collectors
Efficient pumping system
Karanam L. Ramakumar 36
 Very large separation factors possible
Production of large ion currents (space charge
effects)
Strong stable magnetic fields
Suitable material for collectors (proper cooling)
Suitable for producing small amounts of isotopes
60 stable isotopes have been enriched
One of the first methods employed in Manhattan
project in conjunction with thermal diffusion method

Karanam L. Ramakumar 37
 Laser separation methods
Electronic levels of atoms and vibrational levels
molecules differ marginally depending on the
isotopic mass 



υ = R  1 − 1 
e.g. Hydrogen spectrum n
2 n2 
1 2
 

2 4 M1M2
Rydberg constant R = 2π e µ µ = reduced mass =
ch3 M1 + M2
mMH mMD
µH = µD =
MH + m MD + m

→n2
For a given transition n1→
υH = RH = µH For D, λD - λH = 0.1785 nm
υD RD µD

Karanam L. Ramakumar 38
 In the case of molecules, the fundamental frequency of a
diatomic molecule
υ= 1 k
2π µ
For different isotopes µ is different.
∆µ for lighter isotopes is large and for heavier isotopes small
By selecting a suitable wavelength it is possible to selectively
excite and ionise isotopic atoms
Uranium enrichment by lasers
Still at development stage
AVLIS: Atomic Vapour Laser Isotope Separation
MLIS: Molecular Laser Isotope Separation

Karanam L. Ramakumar 39
 AVLIS Process
Reservoir of uranium atoms by heating U metal
U atoms vapour pressure: a few torr
First U-235 atoms are selectively excited and then ionised by
another laser.
Ions are collected by electric or magnetic fields
235U+ Xenon laser
MLIS Process
210 - 310 nm Copper laser
Nitrogen laser 235UF6 molecules are
235U* selectively excited
Dye laser
591.94 nm Nd-Yag laser with IR-laser.
Excited species are
Ground state
irradiated with UV-
laser.
235UF is solid and is condensed 235UF
5 6 → 235UF5 + F
Karanam L. Ramakumar 40
 Performance of different processes for uranium enrichment
Process Separation factor Stages Energy kwh/SWU
Gas diffusion 1.00429 3920 2100
Gas centrifuge 1.25 67 210
Nozzle 1.012 1400 3500
AVLIS 10 1 170
MLIS 33 1 151

Feed: U-235 = 0.00711

Product U-235 = 0.9
Tails: U-235 = 0.002

Karanam L. Ramakumar 41
 Ion exchange enrichment of uranium isotopes

238UO2+2 + 235U(IV)
235UO2+2 + 238U(IV)

K = 1.0015
Ion exchange resin
Uranium loaded on column in H2SO4 medium
Repetitive oxidation, reduction carried out on the column
U(VI) is strongly absorbed
Many process conditions are classified
20 days of continuous operation yielded ~ 3% U-235

Karanam L. Ramakumar 42
 Separation of light isotopes
e.g. Deuterium from Hydrogen

Karanam L. Ramakumar 43
 Mass differences result in small but significant differences
in physico-chemical properties
Property H2 D2 H2O D2O
Boiling point 20.39K 23.67K 373K 374.4K
Freezing point 13.95K 18.65K 273K 276.8K
Molecular weight 2 4 18 20
Density at 200C --- --- 0.991 g/cc 1.106 g/cc

Differences in the behaviour of isotopes due to mass

difference:
Diffusion
Evaporation
Mobility
Reactivity
Karanam L. Ramakumar 44
 Separation factors from vapour pressure ratios at boiling point
Compounds Boiling point (0C) α At boiling point
Ortho-H2/HD -252.9 1.81

3 NH /ND -33.6 1.036

3 3

H2O /D2O 100 1.026

H2O / T2O 100 1.029
20Ne/22Ne -245.9 1.038
14N
2
/ 15N2 -195.8 1.004
H216O/H218O 100 1.0046

Conversion from ortho to para form should be minimised (large

power consumption!!!!)
No paramagnetic or ferromagnetic materials for construction!!

Karanam L. Ramakumar 45
 Distillation methods
Small differences in vapour pressure (boiling point) between the species
containing different isotopes
Separation factor α = x /(1 − x)
y /(1 − y)
x = atom fraction of desired isotope in liquid phase
y = atom fraction of desired isotope in vapour phase
πA πH O πH
αAB = π
B 2 2
πD O πD
H2O + D2O ⇌ 2HDO K = 4 2 2

H2O, D2O, HDO species in liquid phase

  
 xHDO + 2xD O   2yH O + yHDO  πx
α* =  2  2  y= xHDO = xH O.xD O
 2x
 H2O
+ x  y
HDO   HDO
+ 2 y 
D2O 
P 2 2
  

Karanam L. Ramakumar 46
 Depleted liquid hydrogen
Hydrogen rich gas, flux
depleted in D to ammonia
plant

First refrigeratio Secon

coolin n d
Recycle
g coolin
compresso
g
r Joule-Thomson
Normally cooling
closed

First refrigeratio Second

Feed cooling n cooling P
compresso and and
Hydrogen r water nitrogen
from removal removal
ammonia
plant Primary distillation tower
Generalised flow sheet for hydrogen distillation heavy water plants
Karanam L. Ramakumar 47
 HD-Free Exchange reactor
hydrogen Secondary 2HD ⇄ H2 + D2
low pressure towers

Cold natural
hydrogen ⊗
HD + H2
⊗ ⊗ Pure D2

0.028%HD
Heat exchanger
Primary
tower
HD

H2 + HD + D2
5.14%HD

HD-free hydrogen
high pressure Pure D2

Final concentration of deuterium by distillation of liquid hydrogen

Karanam L. Ramakumar 48
 Electrolysis Counter-current process
Once-through process
Feed water

≈
≈
Partially enriched water

≈
≈

Karanam L. Ramakumar 49
 Three-stage cascade of electrolytic cells and exchange towers
C7 C8
T T1, T2, T3 Exchange
F towers
B B
E1, E2, E3 Electrolytic
cells
F Feed water 10000
T1 T3 moles, 0.0148% D
T2
600C
T 9999 moles of
depleted water 0.005# D
C1 C3 C5 B Burners
C2 C4 C6
P P 0.982 moles of Product
E1 E2 E3 99.8% D
C9 C10

C1 0.0598% D, C2 0.0501% D, C3 2.013% D, C4 1.818% D, C5 98.89% D, C6 98.81%

D C7 491.92 moles of 0.101% D, C8 13.818 moles of 3.618% D, C9 492.9 moles of
0.300% D, C10 14.80 moles of 10.0% D

Karanam L. Ramakumar 50
 Chemical exchange methods
HD + H2O(l)
H2 + HDO(l) Catalyst Pt or Ni
K = 3.78 at 250C (Separation factor)
HDS(g) + H2O(l)
H2S(g) + HDO(l)
K = 2.32 at 320C
HD(g) + NH3(l)
H2(g) + NH2D(l) Catalyst KNH2 in NH3
K = 3.60 at 250C (ammonia plant needed!!!)

Water-hydrogen exchange reaction needs catalyst. Finely

divided Pt or Ni
Wetting of catalyst inhibits catalytic exchange
Water has to be in vapour form
Alternatively hydrophobic catalysts may be used.

Karanam L. Ramakumar 51
 Depleted water Waste
Air Sulphur
H2S + ½ O2 →H2O + S

Sulphur
320C recovery
α = 2.32 unit

H2S Mono-thermal water – H2S

Water
exchange

2Al + 3S → Al2S3

Heavy water
product Al2S3 G.S. Process
producer
D2S Al2O3 Al
generator
3D2O + 2Al2S3 → 3D2S + Al2O3
Karanam L. Ramakumar 52
 Feed: Recycle D2S
Natural water
Blower Dual temperature exchange or
bi-thermal exchange process
Cold tower
T = 320C
Avoids reconverting the
α = 2.32 products into initial reactants
to achieve the multiplication
D2S flow effect in the separation factor.
Depleted water
Basis: Temperature
Product D2O flow
dependent property of the
Heat
exchangers equilibrium constant for the
exchange reaction.

Hot tower H2O(l) + HD(g) < = = >

T = 1280C
α = 1.80 HDO(I) + H2(g)
Keq = 3.78 at 250C and 2.60 at
800C

H2O(l) + HDS(g) < = = >

HDO(l) + H2S(g),
Dual temperature Water – H2S Exchange
Girdler – Spevack Process (GS Process) Keq = 2.32 at 32°C and 1.30 at
138°C.
Karanam L. Ramakumar 53
 Ion Migration

Slight differences in velocities of isotopic ions in solution

under an electric field
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 also to be
considered.
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.
Advantage of the fused salt medium: Absence of
ion solvation resulting in larger mass effects in the
migration of isotopic ions.

Separation factor α ∆v/v

∆v is difference in velocities between the isotopes and v
is the mean velocity
Karanam L. Ramakumar 54
 The extent of separation effect between the two isotopes
can also be expressed in terms of relative mass effect
given as
-µ = ∆v /v
∆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 diffusion tends to neutralise the effect partially.

In a typical example, 39K and 41K were separated by the

electromigration of potassium chloride solution in a U-
shaped tube using platinum gauge electrodes,

Karanam L. Ramakumar 55
 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)

Karanam L. Ramakumar 56