2,787,587

iiatented Apr. 2, 1957

2
strong mineral acids are preferred. Examples of such
salts are uranyl chloride, uranous chloride, uranous oxy

2,787,587

chloride, uranyl perchlorate, uranous perchlorate, uranyl

ISOTPE EXCHANGE PRCESS

sulfate, uranous sulfate, and the iike. The nitrates are

undesirable due to the instability of the uranous ion in

Richard W. Woodard, @ak Ridge, Tenn., assignor to .the

United States of America as represented hy the United

nitric acid solution. However, such properties have iong

States Atomic Energy Cossion

been known, and one skilled in the art can readily choose

Application Jniy 26, 1949, Serial No. iii

15 claims. (ci. 24m-_1.5)

'

suitable salts or acids for preparing solutions of adequate

stability for the present process. The solutions employed,
10 whether prepared by dissolving salts in water, by dis
solving oxi'dcs in acid, by partially oxidizing uranous

My invention relates to a method for changing the

isotopic content of an ionic form of an element in solu

tion, and to the utilization of this method for attaining

isotopic enrichment with respect to one or more particu
lar isotopes of the element.
it has previously been found that, in the ca/se of certain

elements, isotopic exchange can take place in solution

between ions of the element in different valence states.

The conditions which make such exchange possible, how

ever, are different for different elements, and no operative
conditions have thus far been found for a great many
of the elements. Even when such exchange has been

found to take place, it has seldom been found possible

to utilize the process for eecting isotopic enrichment

when starting with the naturally occurring isotopic dis

solutions, by partially reducing uranyl solutions, or by

other equivalent processes, may all be termed acid solu
tions of uranous and uranyl ions and will be referred to
as such in the appended claims.

I have found that control of the acidity of the solu

tions employed is essential for attaining practical rates
of isotope exchange. Below a pH of 2, the rate con
stant of the exchange reaction decreases approximately
linearly with pH, and at a pH substantially below l the
rate is so slow as to be of practical utility. ln fact, the

exchange reaction can be practically completely stopped

before equilibrium is attained by strongly acidifying the
solution.

It is unnecessary, for attaining practical exchange

rates, to maintain the pH of the solution above 2.0.

However, in view of the linear relationship between rate

constant and pH it is obvious that for optimum rate the
case of a few elements of low atomic weight, but it has
pH should be as high as possible without encountering
generally been believed that enrichment would be practi 30 interfering side elfects. The upper pH limit has been
cally irnpossible for elements of atomic weight substan
found to be that at which polymeric uranous 'ions are
tially above 40.
formed
in the solution. For any particular solution, this
An object of my present invention is to eect isotopic
upper limit will be 'dependent upon the temperature and
exchange between two forms of uranium of dilerent

tribution.

Such enrichment has been achieved in the

valence states.

Another object of my invention is to provide a process

for achieving isotopic exchange in solution, at a practical

rate, between ionic species of uranium of diierent valence
states.

the concentration of uranous ions in solution. At normal

atmospheric temperatures and concentra-tions of uranous
ions as low as l0~-3 molar, or lower, the upper pH limit
may be as high at 2.5, or even higher. However, for
the preferred concentrations of uranous ions, of the order

of 10-1 molar, and for moderately elevated tempera

A further object is to provide a process for isotopicallly 40 tures,
the upper pH limit will usually be in the neighbor

enriching uranium with respect to one or more particular

isotopes by means of isotopic exchange.

hood of 2.0. l'n any event, the upper limit 'for any par

ticular solution may readily be determined by the appear

A still further object is to provide a semi-continuous
ance of polymeric uranous ions, with resulting changes
multi-stage isotope exchange process for effecting enrich
in the absorption spectrum of the solution. Solutions
ment of naturally occurring uranium with respect to one
45 containing uranyl ions and monomeric uranous ions are
of its isotopes.
_
dark green in color. On the formation of polymeric
Additional objects and advantages of my invention will
uranous
ions the solution darkens and becomes brown
be apparent from the following description.
to almost black, depending upon the concentration. This
in accordance with my present invention, isotopic ex
change may be followed speotrographically, the molar ex
change between uranium ions is effected by contacting
tinction
coeflicients at 400 millimicrons being approxi
50
ions of tetravalent and hexavalen't uranium in an aqueous
mately
7
for the uranyl ion, approximately 0 for mono
acidic solution of carefully controlled acidity and there
meric uranous ions, and approximately 95 for polymeric
after separating the ionic species. When `effecting the eX
uranous ions.
change in this manner, have found that the equilibrium
Since both the isotope exchange reaction and the poly
attained is not strictly a statistical `distribution `of the iso
reaction are (relatively slow und-cr the condi
topic species, but that the lowel- valence state ion is en 55 Inerization
tions of the present process, :the optimum pH will be
riched with respect to the higher atomic `weight isotope,
that at which the .exchange :equilibrium is attained Short
and vice versa. When three or more isotopic species are
ly before the appearance .of the polymeric uranous ions.
present, the highest atomic weight isotope tends to concen
In most cases, however, it will be sufficient .to maintain
trate in the lower valence l-state and the remainder in the
pH between ll.0 and 2.0, ibut preferably between 1.5
higher valence state. Contrary ~.to expectations for an 60 the
and 1.9.
element of such high atomic weight, the 'single-stage en
While the mechanism of the exchange `reaction of the
richment factor thus attainable is sufficiently high .to
present invention has not been established, it has been
make feasible substantially complete isolation of a single
observed that the optimum conditions lfor exchange `cor
isotope by multi-stage operation.
relate
with the optimum conditions for the formation
65
The solutions in which isotopic exchange `is eifected
of hydrolyzedmonomeric uranous ions .in solution. Thus,
in accordance with the present invention may -be aqueous
the ratio of UOH+3 to U+4 yin solutions of uranous
solutions of any uranous and uranyl .salts which are
chloride
up to 10-2 molar, kat about 25 C., has been
known to be stable in solution at the .pH ~values here
found to be represented by the following equation:

inafter discussed. From the standpoints of availability,

ease of preparation for recycle, and convenience in ad 70
justing the pH of the 'resulting so1utions,the salts of 'the

[UOlHH]

3
Similarly, for uranous perchlorate, the equation is:
[Uon+]`_

19g ;:-.[U+] :1i-_pH 144

In a multi-stage process, the separated uranyl uranium

from the preceding stage may be used as the source of
both the uranyl and uranous uranium for the succeeding

enrichment stage (enrichment as to the lighter isotope);

and the uranous uranium from the preceding stage may

Thus, the conditions for satisfactory isotope exchange in

be used as the source of both the uranyl and uranous

accordance with the present invention are the presence of

uranium for the succeeding depletion stage (depletion as

to the lighter isotope). Preferably, however, a multi

substantial concentrations of hydrolyzed monomeric

uranous ions in solution and the absence of substantial

stage enrichment process is carried out by a batch
10 countercnrrent procedure which Vdoes not require oxida
concentrations of polymeric uranous ions.
The total concentration of uranium in the exchange
tion or reduction between stages. An example of one
solution should be as high as possible, to avoid the
stage of such a process is illustrated in the ow diagram

handling of 'large volumes of very dilute solutions. Solu

constituting the accompanying drawing, which is self

bility and polymerization considerations, however, limit

the concentration of uranous ion for the present process

explanatory. In such a process, the exchage solution

for any intermediate stage, for enriching with respect to

to below about 0.5 molar. y The ratio of uranyl to uranous

the lighter isotope, isprepared from the uranyl uranium

ions is not critical, but I generally prefer to employ ap

separated from the preceding stage and from the uranous
Vproximately equal concentrations of both. Suitable
uranium separated from the succeeding stage.
In any such multi-stage operation, the chemical process
solutions are 0.05 to 0.5 molar with respect to both
uranyl and uranous ions, but I prefer to employ solu 20 ing required to convert separated uranium from one stage
tions which are about 0.1 molar with respect to both ions.

into suitable feed solution for an adjacent stage may be

The reactiontemperature for the isotope exchange may

accomplished by processes well known in the art, and such

range from normal atmospheric temperatures, or below,

conversion steps are not claimed as novel herein.
to the normal boiling point of the solution, or even
The following example illustrates the exchange of iso
higher if the solution is maintained under p-ressure. Since 25 topes between uranyl and uranous ion-s of dilerent initial
the use of pressure vessels is inconvenient, it is generally
isotopic constitution, utilizing the differences in radio
preferred to operate within a temperature range of about
activity to follow the exchange reaction:
.2S-75 C. High temperatures will increase the ex
EXAMPLE I
change reaction rate, but may adversely aiect the en
richment equilibrium. For simple exchange reactions I 30 A stock solution was prepared from almost pure Um,
in the form of UCl4, in a concentration of 6.25 grams
therefore prefer to opera-te at elevated temperatures in
U per liter. This solution had a specilic activity of 25,000
order to attain a rapid reaction rate, but for enrichment
counts per minute per milliliter.
purposes I prefer to operate at about 25-30 C., or even
A second stock solution was prepared from uranium
below, in order to attain a favorable enrichment factor.
The isotope exchange of the presen-t invention is photo 35 enhanced in U234 and U235, in the form of UOzClz, alsov
in -a concentration of 6.25 grams U per liter. This solu
sensitive, and the presence of light considerably ac
tion had a specific activity of 132,500 counts per minute
celerates the reaction. Although useful reaction rates are
per milliliter.
attainable when effecting the exchange in the dark, I
Systems were made up by taking 2.0 ml. of each stock
prefer to carry out the reaction in -the light. Any source
of visible light, e. g. daylight or tungsten filament in 40 solution, adding suflicient hydrochloric acid to give the
desired pH, and diluting to a volume of 20.0 ml. The pH
candescent light, is suitable for this purpose. Ultra
of each such exchange solution was then measured po
violet light does not appear to increase the reaction rate
tentiometrically, and a 2.0 ml. Valiquot was withdrawn to
substantially, when used in addition to visible light, but
determine actual initial content of U+1 Vand Ul6 (be
may be employed if desired.
45
cause of partial oxidation of the Ut4 stock solution on
The reaction time for attaining equilibrium lin the ex
change reaction will, of course, `depend on the factors
` Each of the exchange solutions was maintained at 28
such as pH, temperature, and light, which aiect there
C., in the light, and 2.0 ml. aliquots were withdrawn
action rate. When employing the preferred reaction con
ditions, as discussed above, Isuitable reaction times are 50 periodically for analysis. The U+4- content of each ali~
quot was separated` by a conventional cupferron-chloro
from 45 minutes to 120 minutes, with a reaction time of
form extraction. The chloroform solution of the urani
about one hour generally being preferred. In any event
um cupferride was diluted to 10.0 ml. from which a 2.0
the time required to reach equilibrium in the exchange
ml. aliquot was taken for radioactivity determination by
can be determined for any chosen reaction conditions by
periodically sampling the solution and ldetermining the iso 55 conventional counting methods, and a second 2.0 ml.
aliquot was taken for determination of the uranium con
topic content of the uranous uranium and Vof Vthe uranyl
storage).

uranium in the sample.

In carrying out a single stage exchange in accordance
with the present invention the exchange solution is pre
pared in accordance with the above description, using 60
sources of uranyl and uranous ions of either the same or
'dilerent isotopic constitution, as desired. This solution
is then maintained at the chosen pH and temperature,
preferably in the light, until the exchange reaction is sub

stantially complete.

subsequent chemical processing. The uranyl and uranous

components of the solution may then be separated by
conventional methods such as selective precipitationV of
the uranium of one Valence state, or selective extraction
of the uranium of one valence `state by means of organic

solvents using selective chelating agents or the like. Many

'

tent byV conventional colorimetric analysis.

The exchange reaction, effected as above described,
maybe represented as:

U*O2+2+U+4->U*+4+UO2+2
The rate constant, k, for this reaction may be represented
`as;

It is _generally preferable'at this 65

point to acidify the solution, e. g. to about 3N.,'to pre

vent any possible adverse exchange reaction during the

"

'

.k2
where:

Z . -l?fMB-i-BR)

t(A-l-B) B(A--,BR)
l

'

t=tirne in minutes v

A=mierograms U as U*02+2 at t=0

R=W at time=t

suitable separation processes are well known in the art,

and this step of the present process is not claimed as
Quantities A, B, and t are all known, and R is determined
75 by
solving simultaneous equations involving the weight
novel herein.

M4

2,787,587
and radioactivity of the tetravalent uranium inthe system

ment with respect to U235). This was accomplished by

conventional procedures, i. e. precipitating the uranyl ion
The results of the exchange reactions carried out as
as ammonium diur'anate, dissolving the precipitate in aque`
ous nitric acid, reprecipitating with hydrogen peroxide,
described above are shown in Table 1, together with the
calculated rate constant for each `pH zand `reaction time 5 and lcalcining the lat-ter precipitate to produce U03. The
at time=t.

N own-A and B in Table 1 are actually only one-nitieth of the amount of tetravalent and uranyl ion present
ln the original system. These values are employed since the activity and colorlmetric determinations also
represent one-fiftieth of the original system.

The exchange reaction of the above example has also 25 was chlorinated with hexachloropropene to form UCl4,
and the other of which was dissolved in aqueous hydro

been successfully effected using U233 initially in the hexa

valent state, using U233 initially in the tetravalent state,
and using U02SO4 and U(S04)2 in place of U02Clz and

chloric acid and evaporated to dryness to produce

UCllr.

tained were then dissolved in water, each at a concentra

U0zCl2.XH20.

The uranous and uranyl salts thus ob

The following example illustrates the utilization of the 30 tion of 2% U, to form the exchange solution for the suc~
ceeding enrichment stage.
exchange reaction .of the present invention in a multi
The above procedure was repeated, with respect to the
stage process for the isotopic enrichment of natural

uranium:

oxalate filtrate, for seven more stages, to make a total of

nine enrichment stages, each stage involving a 50% vol

EXAMPLE II

35

A quantity of uranium oxide (U03) of known isotopic

ume reduction.

The uranous oxalate 'precipitate from the initial stage,

as described above, was utilized to prepare the feed yfor
the rst of a series of depletion stages (depletion with

concentration. (normal at the start of a run) was divided

into two equal portions. One of these was chlorinated
to UCLr with hexachloropropene, the other was prepared

respect to Um). This, again, was accomplished by well

as U02Cl2,XH20 by dissolving U03 in hydrochloric acid 40 known methods, i. e., igniting the oxalate to produce
and evaporating to dryness on the hotplate. The two
U30s, dissolving the U30s in nitric acid, precipitating the

salts, UClt and U02C12, were then dissolved in a sutlicient

quantity of `Water- to give a 4% uranium solution, i. e.
2% with respect to U+4 and v2% U as U02+2. The pH
of the solution was checked at this point and usually it
was 1.54.6, which is within the preferred range forex
change. Suicient time, usually about one hour, was
allowed for the system to .come to equilibrium at 28-30
C. The exchange reaction was stopped at this point by

uranium from the nitric acid solution with hydrogen per

oxide, and calcining the latter precipitate to produce U03.
The U03 was then divided into two equal parts, one of

which was chlorinated with hexachloropropene to pro

duce UCl4, and the other of which was dissolved in aque
ous hydrochloric acid and evaporated to dryness to pro~

duce U02Cl2JU-I2O. The resulting uranous and uranyl

salts were then dissolved in water, each at a concentration

the addition of a Sueient quantity of hydrochloric acid

of 2% U, to form the exchange solution for the succeed

to raise the normality to 3N. A five percent excess over

the theoretical amount of oxalie acid necessary to pre

ing depletion stage.

cipitate all U+4 ion was added and the solution stirred

This procedure was then repeated, with respect to the

oxalate precipitate, for eight more stages, to make a total

to aid in the formation et an easily filtered uranous oxa

late precipitate. The oxalate precipitate was washed sev

ume reduction.

eral times with dilute. HC1 containing oxalic acid, combin

ing these washings with the original lti te,

A summary or" the above enrichment runs is given in

Table 2, and a summary of the depletion runs in Table 3.

The filtrate from the oxalate precipitation was utilized

to prepare the feed for the next enrichment stag@ (enrich

In each case initial, intermediate, and iinal assays for

of nine depetion stages, each stage involving a 50% vol

U235 are included.

Table 2
ENRICHMENT RUNS

Total U in grams

As UH

As U02

Total
Volume o
System
(M1.)

396
198
96
4T
23
10. S

399
198
96
46
22. 5
10. 8

40, 000
20, 000
9, 600
4, 600
2, 200
1, 080

l. 55
l, 68
1. 53
l. 55
1. 55
1. 58

5.. 5_ `

5. 2

700

1. 40

3. 5
1. 6

3. 5
1. 6

350
160

1. 52

Stage

pH

Time of
Stand

(Mln.)

1. 49

M l. Conc.
Oxalic
HC1 Add. Acid Add
at end of
to PPT
Exchange
U+4 (g.)

Assayof
Samples,
Percent
U2

__

affamati
Table 3
DEPLETION RUNS

Stage

Total U in grams
I

Total Vol.

of system,

pH

Ml.

As U'H

As U02+2

399
164
s2
47
22. 4
12. 8
5. 6
2. 7

399
145
54
32
18. 4
10. 9
4. 8
2. 4

20, 000
7, 750
4,000
1, 975
l, 018
593
308
153

1. 60
1. 55
1. sa
1. 55
1. 5l
1. 55
1. 57
1. 58

l. 6

l. 5

78

l. 51

from the assays of either the enrichment runs or the de

uranyl ions and uranous ions which comprises digesting

an aqueous hydrochloric acid solution of uranyl ions and

pletion runs of the above example. From this it may be

monomeric hydrolyzed uranous ions for a period of about

A -stage separation factor of 1.0012 may be calculated

seen that by greatly increasingv the number of stages 20 one hour at a temperature of 25~75 C. and in the pres
U335 may be substantially completely separated from n ence of light, and thereafter separating the uranyl and
uranous components of said solution'.l
natural uranium by the process of the present invention.
__ 6. A process for isotopically enriching, with respect to
Obviously, however, for such a greatly increased number
`a lighter isotope, uranium initially containing a plurality
of stages a 50% volume reduction per stage would be
very undesirable. This may be avoided by employing a 25 of isotopes, which comprises forming from said uranium
counter-current batch procedure such as hereinbefore re
ferred to and illustrated, as to one stage, in the accom

an aqueous acidic solution of uranyl and uranous ions,

After a countercurrent cascade

digesting said solution- at a pH of 1.0-2.0, separating the

uranyl and uranous components of the digested solution,

of this type has reached operating equilibrium, the uranyl

forming from the separated isotopically enriched uranyl

panying ow diagram.

uranium may be passed stagewise up the cascade, and the 30 componentpa fresh aqueous acidic solution of uranyl and
uranous ions, and repeating said digesting and separating
uranous uranium stagewise down the cascade Without the
necessity for -a substantial volume change from stage to
7. The process of claim 6 in which the initial plurality
stage.
of isotopes comprises essentially U235 and U23".
It will be apparent that the procedure of Example VII
8. The process of claim 6 in which the initial plurality
may be utilized for the separation of isotopes other than 35
of isotopes consists essentiallyof U234 and U23.
U235. For'example, natural uranium which has been de
steps,

pleted of U235 by the electromagnetic separation process,

'

__

9."A process for isotopically enriching, with respect to

a lighter isotope, uranium initially containing a plurality

and subsequently stored for a long period _of time, con
of isotopes, which comprises forming from said uranium.
tains substantial quantitiesof U234 in addition to the
otherwise substantially pure U238. These two isotopes, 40 an aqueous mineral acid solution about 0.1 molar with
respect to uranyl ions and about 0.1 molar with respect
both of which have recognized utility, obviously can be
to uranous ions, digesting said solution for about one
successfully separated by the enrichment process illus
hour at a temperature of 25-75 C. and in the presence
trated in connection with the lseparation of U235.
of light, while maintaining the pH of said solution be
In general, it may be said that the above examples are
tween 1.5 and 1.9, separating the uranyl and uranous
merely illustrative and should not be construed as limit
_ components of the digested solution, forming from the
ing the scope of my invention. Numerous other isotope
separated isotopically enriched uranyl component a fresh
combinations may be separated, various other exchange
mineral acid solution of uranyl and uranous ions, and
reaction conditions may be employed, and many other
repeating said digesting and separating steps. '
interstage chemical conversion steps may be utilized,
110. A process for isotopically enriching and depleting,
within the scope of the foregoing description. The scope 50
with respect to a'lighter isotope, uranium initially con
of my invention should be understood to be limited only
taining a plurality of isotopes, >which comprises forming
as indicated by the appended claims.
from said uranium an aqueous mineral acid solution of
I claim:
uranyl and monomeric hydrolyzed uranous ions, digesting
l. A process for effecting isotope exchange between
said solution' to eiect isotope exchange, separating the
uranyl ions and uranous ions which comprises digesting
an aqueous acidic solution of uranyl ions and uranous
ions at a pH of 1.0-2.0.

uranyl and uranous components of the digested solution,

utilizing the separated isotopically enriched uranyl com

- 2. Aprocess forv effecting isotope exchange between

ponent as the source of uranyl ions for a fresh aqueous

uranyl ions and uranous ions which comprises digesting

mineral acid- solutionof-uranyl Vions vand> monomeric

an aqueous mineral acid solution of uranyly ions and 60 hydrolyzed uranous ions, and repeating said digesting and
separating steps; utilizing the separated isotopically de
uranous ions at a temperature of 25-75" C. and-_in- the

presence of light, while maintaining the pH of said solu

tion between 1.5 and 1.9..

pleted uranous component from said first digesting step

_ as the source of uranous ions for a fresh aqueous mineral

_acid solution ofuranyl ions and monomeric hydrolyzed

_3. A lprocess for effecting isotope 'exchangebetween _
uranyl ions and uranous ions which comprises digestingV 65 uranous ions, and repeating said digesting and separating
an aqueous acidic solutionof uranyl ions and. uranous _
ions at a pH above '1.0 and below the -pH at which poly- _ _

meric uranous ions are formed in said solution.'

I 4. A process for effecting isotope `exchange betweenv

uranyl ions vand uranous ions which comprises digesting@

steps._

____

___

__

11. The process of claim 10 in which the initial plu

l rality of isotopes comprises essentially U235 and U233~
12, The lprocess of claim 10 in which the initial plu
rality of isotopes'consists essentially of U234 and U23".

anaqueous acidic solution of uranyl ions and monomeric '-v

13. A process for isotopically enriching and depleting,

hydrolyzed uranous ions at a temperature of 'Z5-75 _C2 _

with- respect to a lighterv isotope, uranium initially con

_ _ _

taining a plurality Vof isotopes, which comprises forming

from said uraniuman vaqueous hydrochloric acid solution

5. A process for effecting isotope exchange between

about 0.1 molar with respect to uranyl ions and about

andin the presence of light and thereafter separating the f.

uranyl and uranous components of 4said solution.

wams?

9
0.1 molar with respect to uranons ions, digesting said
solution for about one hour at a temperature of 25-30 C.

10
aqueous hydrochloric acid solution of uranyl and uranous

ions, and repeating said digesting and separating steps.

14. The process of claim 13 in which the initial plu

in the presence of light while maintaining the pH of said
rality of isotopes comprises essentially U235 and U2.
solution between 1.5 and 1.9, separating the uranyl and
15. The process of claim 13 in which the initial plu
uranous components of the digested solution, utilizing 5

the separated isotopically enriched uranyl component as

the source of uranyl ions for a fresh hydrochloric acid

solution of uranyl ions and uranous ions, and repeating

said digesting and separating steps; utilizing the separated

rality of isotopes consists essentially of U234 and U23".

References Cited in the file of this patent

Friend: Textbook of Inorganic Chemistry, vol. VII,

isotopically depleted uranous component from said first 10 part III, p. 288; published in 1926 by Charles Grin and
digesting step as the source of uranous ions for a fresh

Co., Ltd., London. (Copy in Scientific Library.)